Formamide group-containing copolymer, process for producing the same, and thermoplastic resin composition containing the same

ABSTRACT

A novel formamide group-containing copolymer, or a salt thereof, which can be used as a high-molecular weight amino reagent, a starting material for functional high-molecular weight compounds, a starting material for adhesives, a polymer compatibilizer, a resin modifier, etc., and can undergo hydrolysis to give a copolymer containing a primary amino group, and a novel copolymer containing a primary amino group obtained by hydrolysis.

FIELD OF THE INVENTION

The present invention relates to a formamide group-containing copolymerand a process for producing the same. More particularly, the presentinvention relates to a novel formamide group-containing copolymer whichcan be used as a high-molecular weight amino reagent, a startingmaterial for functional high-molecular weight compounds, a startingmaterial for adhesives, a polymer compatibilizer, a resin modifier, etc.and can undergo hydrolysis to give a copolymer containing a primaryamino group, a novel copolymer containing a primary amino group obtainedby hydrolysis, and a process for producing the same with goodefficiency. Also, the present invention relates to a thermoplastic resincomposition, and more particularly to a thermoplastic resin compositioncomprising the above-mentioned formamide group-containing copolymerhaving two or more kinds of specified thermoplastic resins blendedtherewith, which not only enhances the miscibility between the resinsbut also is superior in the face impact strength, Izod impact strengthexternal appearance, and hue.

BACKGROUND OF THE INVENTION

Heretofore, high-molecular weight compounds containing primary aminogroups in their side chains have been effectively utilized in variousindustrial fields because of their high reactivity, that is, becausethey can easily react with functional groups such as aldehyde, ketone,alkyl halide, isocyanate, thioisocyanate, active double bond, epoxycompound, cyanamide, guanidine, urea, acid, acid anhydride, and acylhalide.

As such high-molecular weight compounds containing primary amino groupsin their side chains, there have been heretofore known polyvinylamineproduced by hydrolysis of poly-N-vinylacetamide or poly-N-vinylformamideand polyallylamine produced by polymerization of a hydrochloride ofallylamine.

However, in the case where these methods are used to prepare ahigh-molecular weight compound, although a polymer or copolymercontaining a primary amino group can be obtained, its molecular weightis not so great as intended, and these methods require radicalpolymerization of an amine or an amine precursor as a monomer whichlimits the kind of monomers to be copolymerized therewith. Therefore,these high-molecular weight compounds may not fully exert their effectsin some applications.

As examples of copolymers containing amino groups in their side chains,there are disclosed in JP-A-2-135214 and JP-A-2-135215 (the term "JP-A"as used herein means an "unexamined published Japanese patentapplication") a copolymer obtained by imidation of a styrene-maleicanhydride copolymer with a mixture of primary and secondary diaminessuch as p-aminophenol and ethylaminoethylamine. It is proposed thatthese copolymers be used as potential epoxy hardeners. These copolymersalso contain ethylamino groups in their side chains. However, the sidechain functional groups thus obtained are secondary amino groups. Ingeneral, secondary amino groups have less general-purpose propertiesthan primary amino groups. In this respect, these copolymers are notdesirable.

Examples of copolymers in which primary amino groups have been probablyunexpectedly incorporated partially in their chains include thosedisclosed in JP-A-64-70595 and JP-A- 64-85246, and U.S. Pat. No.4,137,185. That is, these copolymers are obtained by reacting a maleicanhydride-grafted ethylene propylene copolymer which is obtained bygrafting an ethylene-propylene copolymer with maleic anhydride, with apolyamine containing at least two primary amino groups such asdiethylenetriamine, ethlenediamine, and hexamethylenediamine so that itundergoes imidization. However, it is thought that the reaction of amaleic anhydride-grafted ethylene propylene copolymer with apolyfunctional polyamine generally involves a crosslinking reaction nota little during as well as after the reaction. If any crosslinkingreaction occurs during the reaction, it may often cause a rise in theviscosity of the reaction mixture and, hence, gelation thereof,disabling the continuance of the reaction.

Therefore, in these conventional techniques, it has been designed toend-cap primary amines present after imidization with acetic anhydride,n-octenylsuccinic anhydride, or the like for the purpose of inhibitingthe thickness rise with a lapse of time due to the crosslinkingreaction.

Further, JP-A-2-36248 suggests the reaction of an unsaturated acidanhydride-graft modified polyolefin with a diamine. However, thisreference gives no clear statement of specific preparation methods andreaction products, and the present inventors' experiences show thatcrosslinking and gelation are unavoidable according to known methods.

As examples of the reaction of a maleic anhydride copolymer or a maleicanhydride-grafted ethylene propylene copolymer with a primary diamine,there are disclosed methods in JP-A-60-240749, JP-A-64-31864,JP-A-63-146928, JP-A-63-235365, and JP-A-63-199755. However, all thesemethods are intended for the imide crosslinking of an acid anhydridegroup with two primary amino groups in a solvent-free resin.

It is theoretically possible to undergo imidization with a primarydiamine to form primary amino groups in side chains without causing anycrosslinking reaction by raising the molar ratio of primary aminogroup/succinic anhydride group in the imidation reaction to such anextent that gelation caused by the crosslinking reaction can besubtantially neglected. However, this idea is not practical.

Some of the present inventors previously proposed an improvedpreparation method which overcomes these drawbacks accompanied by theconventional techniques and a novel copolymer obtained thereby (JapanesePatent Application No. Hei. 3-85735). In this proposal, there issuggested a method which comprises reacting a partial salt of a diaminewith an acid, with a succinic anhydride group-containing copolymer andthen allowing a base to contact with the reaction product to regeneratean amino group.

It has heretofore been considered to be technically difficult to obtaina copolymer with an excellent hue without causing any crosslinkingreaction by allowing diamines to act on a polyfunctional copolymercontaining a substituted or unsubstituted succinic anhydride group as afunctional group to cause a high-molecular weight modification reactionto incorporate primary amino groups in side chains.

The present invention was worked out to overcome these difficulties.

SUMMARY OF THE INVENTION

The present inventors have made extensitive studies to overcome thesedrawbacks of the conventional techniques. As a result, it has been foundthat a novel formamide group-containing copolymer can be obtained by aprocess which comprises reacting a compound having a recurring unitderived from styrene, olefins or derivatives thereof, a recurring unitderived from dienes such as butadiene, and a recurring unit derived fromacid anhydrides such as maleic anhydride, with a salt of a specificprimary diamine in the presence of a formyl group-containing compoundsuch as formamide, to effect imidation and/or amidation, and thendeacidifying the product with a base, or by imidation and/or amidationof the above-mentioned copolymer with a reaction product obtained byreacting a primary diamine with a formyl group-containing compound suchas formamide and that a composition suitable for the above-mentionedobjects can be obtained by hydrolysis of such a novel copolymer. Thepresent invention has been worked out on the basis of this knowledge.

That is, the present invention provides a copolymer or a salt thereofcontaining in the molecule thereof:

(A) from 20 to 99.8 mole % of a recurring unit represented by formula(I),

(B) from 50 to 0 mole % of a recurring unit represented by formula (II),and

(C) a recurring unit containing a unit represented by formula (III), (D)a recurring unit containing a unit represented by formula (IV), and (E)a recurring unit containing a unit represented by formula (V) in a totalamount of from 60 to 0.2 mole %, provided that the amount of saidrecurring unit (C) is at least 0.2 mole %: ##STR1## wherein R¹ and R²each independently represents a hydrogen atom, an alkyl group havingfrom 1 to 10 carbon atoms, a cycloalkyl group having from 3 to 8 carbonatoms, an aryl group having from 6 to 10 carbon atoms, an alkenyl grouphaving from 2 to 4 carbon atoms, an alkoxy group having from 1 to 4carbon atoms, an alkoxycarbonyl group having from 1 to 18 carbon atoms,an alkylcarboxyl group having from 1 to 17 carbon atoms, in the allkylportion thereof an alkylcarbonyl group having from 1 to 6 carbon atoms,an arylcarbonyl group having from 6 to 8 carbon atoms, a halogen atom,or a nitrile group; R³ and R⁴ each independently represents a hydrogenatom, an alkyl group having from 1 to 4 carbon atoms, an alkenyl grouphaving from 2 to 4 carbon atoms, or a halogen atom; R⁵ and R⁶ eachindependently represents a hydrogen atom, an alkyl group having from 1to 6 carbon atoms, or an aryl group having from 6 to 8 carbon atoms; R⁷represents an alkylene group having from 1 to 12 carbon atoms, acycloalkylene group having from 5 to 17 carbon atoms, an arylene grouphaving from 6 to 12 carbon atoms, an arylalkylene group having from 7 to12 carbon atoms, or a polyoxyalkylene group having from 4 to 30 carbonatoms; R¹ to R⁷ may be each the same or different in each of therecurring units; and X¹ and X² each independently represents NH₂ orNH-CHO.

The present invention also provides a process for producing theabove-mentioned copolymer or a salt thereof, which comprises reacting acopolymer containing in the molecule thereof:

(a) from 20 to 99.8 mole % of a recurring unit represented by formula(I),

(B) from 50 to 0 mole % of a recurring unit represented by formula (II),and

(C') from 60 to 0.2 mole % of a recurring unit containing a unitrepresented by formula (VI): ##STR2## wherein R⁵ and R⁶ are as definedabove, with a salt of a diamine represented by formula (VII):

    H.sub.2 N--R.sup.7 --NH.sub.2                              (VII)

wherein R⁷ is as defined above, in the presence of at least one formylgroup-containing compound selected from formamide, formic acid, andderivatives thereof, bringing the reaction product into contact with abase to undergo deacidification (process (a)).

The present invention further provides a process for producing theabove-mentioned copolymer or a salt thereof, which comprises reacting acopolymer containing in the molecule thereof:

(A) from 20 to 99.8 mole % of a recurring unit represented by formula(I),

(B) from 50 to 0 mole % of a recurring unit represented by formula (II),and

(C') from 60 to 0.2 mole % of a recurring unit containing a unitrepresented by formula (VI), with a product obtained by reacting adiamine represented by formula (VII) with at least one formylgroup-containing compound selected from formamide, formic acid, andderivatives thereof (process (b)).

The present invention still further provides a process for producing acopolymer and a salt thereof containing in the molecule thereof:

(A) from 20 to 99.8 mole % of a recurring unit represented by formula(I),

(B) 50 to 0 mole % of a recurring unit represented by formula (II), and

(D) a recurring unit containing a unit represented by formula (IV) and(E) a recurring unit containing a unit represented by formula (V) in atotal amount of 60 to 0.2 mole %, provided that the amount of saidrecurring unit (D) is at least 0.2 mole % and that X¹ and X² eachrepresents NH₂, which comprises hydrolyzing the above-mentionedcopolymer under acidic conditions (process (c)) as well as the copolymerthus obtained or a salt thereof.

The present invention even further provides a thermoplastic resincomposition, comprising as main components 100 parts by weight of amixture of (i) from 5 to 95% by weight of a thermoplastic resincontaining a functional group capable of reacting with an amino groupand (ii) from 95 to 5% by weight of an olefinic polymer and/or astyrenic polymer; and (iii) from 0.05 to 20 parts by weight of acopolymer or a salt thereof containing in the molecule thereof:

(A) from 20 to 99.8 mole % of a recurring unit represented by formula(I);

(B) from 50 to 0 mole % of a recurring unit represented by formula (II);and

(C) a recurring unit containing a unit represented by formula (IV), (D)a recurring unit containing a unit represented by formula (IV), and arecurring unit containing a unit represented by formula (V) in a totalamount of from 60 to 0.2 mole %, provided that the amount of saidrecurring unit C is at least 0.2 mole %.

DETAILED DESCRIPTION OF THE INVENTION

The formamide group-containing copolymer of the present invention(including a salt thereof hereinafter) is a novel copolymer containing arecurring unit (A) represented by formula (I), a recurring unit (B)represented by formula (II), a recurring unit (C) containing a unitrepresented by formula (III), a recurring unit (D) containing a unitrepresented by formula (IV), and a recurring unit (E) containing a unitrepresented by formula (V) (the recurring units (B), (D) and (E) are notessential), which may be a random, block or graft copolymer. Asmentioned above, the proportion of the recurring units (A) and (B) inthe copolymer are from 20 to 99.8 mole %, preferably from 45 to 99 mole%, and from 50 to 0 mole %, preferably from 40 to 0 mole %, respectivelybased on the total amount of the recurring units (A), (B), (C), (D) and(E); and the sum of the proportion of the recurring units (C), (D) and(E) is in the range of from 60 to 0.2 mole %, based on the total amountof the recurring units (A), (B), (C), (D) and (E), provided that theproportion of the recurring unit (C) is 0.2 mole % or more and that theamount of the recurring units (D) and (E) each may be 0 mole %. In thesum of the proportion of the recurring units (C), (D) and (E), theproportion of the recurring unit (C) is preferably in the range of from50 to 1 mole %, the proportion of the recurring unit (D) is preferablyin the range of 40 mole % or less, and the proportion of the recurringunit (E) is preferably in the range of 40 mole % or less. If theproportion of the recurring unit (C) exceeds 60 mole %, it isdisadvantageous in that the resulting copolymer exhibits deterioratedmechanical properties. On the contrary, if the proportion of therecurring unit (C) falls below 0.2 mole %, the features of the formamidegroup-containing copolymer of the present invention cannot besufficiently developed.

The copolymer of the present invention basically comprises theabove-mentioned recurring units (A), (B), (C), (D) and (E) but mayfurther comprise other recurring units in a small amount.

The molecular weight of the copolymer of the present invention is notspecifically limited but is normally in the range of from 3,000 to500,000 as calculated in terms of viscosity average molecular weight.This range corresponds to a vicosity range of from 10 to 50,000 cpsobtained when dissolving the formamide group-containing copolymer in agood solvent such as toluene, xylene, cumene, tetralin,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, acetone, and methylethyl ketone in a proportion of 10% by weight.

The copolymer of the present invention is characterized in that itcontains in side chains of the recurring unit (C) formamide groupsor/and primary amino groups via an imide group or an amide group.Examples of the copolymer of the present invention include thosecomprising a salt formed when the above-mentioned primary amino group isbonded to an acid such as sulfuric acid, a sulfonic acid (e.g.,benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid), ahalogenic acid (e.g., hydrochloric acid, hydrofluoric acid, hydrobromicacid), nitric acid, boric acid, and phosphoric acid.

The recurring unit (A) is represented by formula (I) wherein R^(l) andR² may be the same or different and each independently represents ahydrogen atom; an alkyl group containing from 1 to 10 carbon atoms,preferably from 1 to 4 carbon atoms; a cycloalkyl group containing from3 to 8 carbon atoms, preferably from 3 to 6 carbon atoms; an aryl groupcontaining from 6 to 10 carbon atoms, preferably from 6 to 9 carbonatoms; an alkenyl group containing from 2 to 4 carbon atoms (e.g.,vinyl, allyl); an alkoxy group containing from 1 to 4 carbon atoms; analkoxycarbonyl group containing from 1 to 18 carbon atoms, preferablyfrom 1 to 8 carbon atoms; an alkylcarboxyl group containing from 1 to 17carbon atoms, preferably from 1 to 3 carbon atoms, in the alkyl portionthereof; an alkylcarbonyl group containing from 1 to 6 carbon atoms,preferably 1 to 4 carbon atoms; an arylcarbonyl group containing from 6to 8 carbon atoms; a halogen atom (e.g., chlorine, bromine); or anitrile group. R^(l) and R² may be each the same or different in each ofthe recurring units. In other words, examples of formula (I) includethose wherein one of the recurring unit (A) is an ethylene unit (R¹ andR² each is a hydrogen atom at the same time) and the other is apropylene unit (R¹ is a hydrogen atom, and R² is a methyl group).

The recurring unit (B) is represented by formula (II) wherein R³ and R⁴each independently represents a hydrogen atom; an alkyl group containingfrom 1 to 4 carbon atoms (e. g., methyl, ethyl); an alkenyl groupcontaining from 2 to 4 carbon atoms (e.g., vinyl, allyl); or a halogenatom (e.g., chlorine, bromine). As in the case of R¹ and R², R³ and R⁴may be each the same or different in each of the recurring units.

The recurring unit (C) contains a unit represented by formula (III)wherein R⁵ and R⁶ each independently represents a hydrogen atom; analkyl group containing from 1 to 6 carbon atoms, preferably from 1 to 2carbon atoms; or an aryl group containing from 6 to 8 carbon atoms; andR⁷ represents an alkylene group containing from 1 to 12 carbon atoms,preferably from 1 to 8 carbon atoms (e.g., methylene, ethylene,propylene, tetramethylene, hexamethylene); a cycloalkylene groupcontaining from 5 to 17 carbon atom, preferably from 6 to 10 carbonatoms (e.g., cyclohexylene, methylenecyclohexylmethylene); an arylenegroup containing from 6 to 12 carbon atoms (e.g., phenylene,oxydiphenylene); an arylalkylene group containing from 7 to 12 carbonatoms, preferably from 8 to 10 carbon atoms (e.g., xylylene); or apolyoxyalkene group containing from 4 to 30 carbon atoms, preferablyfrom 4 to 15 carbon atoms (e.g., polyoxymethylene, polyoxypropylene). Asin the case of R¹ and R², R⁵ and R⁶ may be each the same or different ineach of the recurring units.

Further, the recurring unit (C) may be a unit represented by formula(III) itself, or may be a unit represented by formula (III-A) obtainedby grafting the unit represented by formula (III). ##STR3## wherein R⁵,R⁶ and R⁷ are as defined above; R⁸ to R¹⁰ have the same meaning as R¹and R² or each independently represents a hydrogen atom; an alkyl groupcontaining from 1 to 10 carbon atoms, preferably from 1 to 4 carbonatoms; an alkenyl group containing from 2 to 4 carbon atoms (e.g.,vinyl, allyl); a cycloalkyl group containing from 3 to 8 carbon atoms,preferably from 3 to 6 carbon atoms; an aryl group containing from 6 to10 carbon atoms, preferably from 6 to 9 carbon atoms; an alkoxy groupcontaining from 1 to 4 carbon atoms; an alkoxycarbonyl group containingfrom 1 to 18 carbon atoms, preferably from 1 to 8 carbon atoms; analkylcarboxyl group containing from 1 to 17 carbon atoms, preferablyfrom 1 to 3 carbon atoms, in the alkyl portion thereof; an alkylcarbonylgroup containing from 1 to 6 carbon atoms, preferably from 1 to 4 carbonatoms; an arylcarbonyl group containing from 6 to 8 carbon atoms; ahalogen atom (e.g., chlorine, bromine); or a nitrile group; R¹¹ is notpresent (i.e., represents a mere bond) or represents a methylene groupor an ethylene group; and R¹² represents a hydrogen atom or an alkylgroup containing from 1 to 10 carbon atoms, preferably from 1 to 8carbon atoms. As in the case of R¹ and R², R⁵ to R¹² may be each thesame or different in each of the recurring units. The suffix nrepresents an integer of from 1 to 10, preferably from 1 to 3. When n isplural, i.e., 2 or more, R⁵, R⁶ and R⁷ which are each present in anumber corresponding to n may be each the same or different.

The recurring unit (D) contains a unit represented by formula (IV). Therecurring unit (E) contains a unit represented by formula (V). In theseformulae, R⁵ to R⁷ are as defined in formula (III). X¹ and X² eachrepresents NH₂ or NH-CHO and may be the same or different.

The recurring unit (D) may be a unit represented by formula (IV) itselfor may be a unit represented by formula (IV-A) obtained by grafting theunit represented by formula (IV). The recurring unit (E) may be a unitrepresented by formula (V) itself or may be a unit represented byformula (V-A) obtained by grafting the unit represented by formula (V).##STR4## wherein R⁵ to R¹², X¹, X² and n are as defined above.

The preparation of the copolymer of the present invention is not limitedto specific processes but may be accomplished by various processes. Inaccordance with the above-mentioned processes (a) and (b), the copolymerof the present invention can be prepared more efficiently.

The copolymer comprising the recurring units (A), (B) and (C') as thestarting materials of the process of the present invention can beprepared by subjecting monomers giving recurring units represented byformulae (I) and (II) with a monomer giving a recurring unit representedby formula (VI) to ordinary radical polymerization or ionicpolymerization, or by subjecting monomers giving recurring unitsrepresented by formulae (I) and (II) to ordinary radical polymerizationor ionic polymerization, and then allowing a monomer giving a recurringunit represented by formula (VI) to undergo graft reaction with thepolymerization product.

Specific examples of monomers giving the recurring unit (A) representedby formula (I) include various compounds such as olefins (e.g.,ethylene, propylene, 1-butene, isobutylene, 1-octene), cyclic olefins(e.g., cyclopentene, cyclohexene, cyclooctene), styrenes (aromatic vinylcompounds) (e.g., styrene, α-methylstyrene, vinyltoluene,p-t-butylstyrene), vinyl esters (e.g., vinyl acetate, vinyl butyrate,vinyl stearate), vinyl ethers (e.g., methyl vinyl ether, ethyl vinylether), halogeno olefins (e.g., vinyl chloride, vinylidene chloride),acrylic or methacrylic acid esters (e.g., methyl (meth)acrylate, ethyl(meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl(meth)acrylate, decyl (meth)acrylate, octadecyl (meth)acrylate,methoxyethyl (meth)acrylate), nitriles (e.g., acrylonitrile,methacrylonitrile), and vinyl ketones (e.g., methyl vinyl ketone, phenylvinyl ketone). These monomers can be used singly or in combination.Preferred among these monomers are ethylene, propylene, styrene, methylvinyl ether, isobutylene, vinyl acetate, and (meth)acrylic acid esters.Further, hydrogenated products of polymers of isoprene, butadiene, etc.can be used.

Specific examples of monomers giving the recurring unit (B) representedby formula (II) include conjugated dienes such as butadiene, isoprene,and chloroprene. These conjugated dienes can be used singly or incombination. Preferred among these monomers are butadiene and isoprene.

Examples of the recurring unit (C') containing a unit represented byformula (VI) include anhydrous unsaturated dicarboxylic acids, such asmaleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic acid,ethylmaleic anhydride, phenylmaleic anhydride, and itaconic anhydride,obtained by subjecting a monomer giving the recurring unit (A) and amonomer giving the recurring unit (B) to a known copolymerization, andthen treating the resulting copolymer with a known peroxide orinitiator.

The recurring unit (C') may be a unit represented by formula (VI) itselfor may be a unit represented by formula (VI-A) obtained by grafting theunit represented by formula (VI). ##STR5## wherein R⁵, R⁶, R⁸ to R¹²,and n are as defined above.

The recurring unit (C') containing a unit represented by formula (VI-A)can be formed by subjecting a monomer giving the above-mentionedrecurring unit (A) and a monomer giving the above-mentioned recurringunit (B) to known copolymerization, and then allowing the resultingcopolymer to undergo a graft reaction with an anhydrous unsaturateddicarboxylic acid such as maleic anhydride, methylmaleic anhydride,1,2-dimethylmaleic acid, ethylmaleic anhydride, phenylmaleic anhydride,and itaconic anhydride in the presence of a known peroxide or initiator.(A) preferred grafting monomer is maleic anhydride. The graft reactionproceeds as the grafting monomer such as maleic anhydride is connectedto the portion of the recurring unit (A) or (B). As the startingmaterial of the process of the present invention including the recurringunit (C') there can be also used a polymer commercially available as apolymer grafted with the above-mentioned anhydrous unsaturateddicarboxylic acid (e.g., maleic acid-modified EPR, maleic acid-modifiedSEBS).

Thus, examples of the copolymer containing the recurring units (A), (B)and (C') as the starting material of the process of the presentinvention include a styrene-maleic anhydride copolymer, anethylene-maleic anhydride copolymer, a propylene-maleic anhydridecopolymer, an ethylene-propylene-maleic anhydride copolymer, anisobutylene-maleic anhydride copolymer, a methyl vinyl ether-maleicanhydride copolymer, a styrene-isoprene-maleic anhydride copolymer, anethylene-maleic anhydride-ethyl acrylate copolymer, an ethylene-maleicanhydride-methyl acrylate copolymer, an ethylene-vinyl acetate-maleicanhydride copolymer, and a styrene-butadiene-maleic anhydride copolymer.Further examples include copolymers obtained by allowing polymers orcopolymers obtained by allowing polymers or copolymers such aspolyethylene, polypropylene, polyisoprene and hydrogenated productsthereof, polybutadiene and hydrogenated products thereof, chloroprenerubber and hydrogenated products thereof, nitrile rubber andhydrogenated products thereof, ethylenepropylene copolymers,ethylene-(meth)acrylic acid ester copolymers, styrene-isoprenecopolymers and hydrogenated products thereof, and styrene-butadienecopolymers and hydrogenated products thereof (the copolymers may be anyof random copolymers, block copolymers and alternating copolymers) toundergo a graft reaction with an anhydrous unsaturated dicarboxylic acidsuch as maleic anhydride, methylamaleic anhydride, ethylmaleicanhydride, and itaconic anhydride. However, the present invention shouldnot be construed as being limited thereto.

In accordance with the process (a) of the present invention, thecopolymer comprising the recurring units (A), (B) and (C') thus preparedis allowed to undergo a reaction with a salt of a primary diaminerepresented by formula (VII) in the presence of at least one formylgroup-containing compound selected from formamide, formic acid, andderivatives thereof. As mentioned above, the formyl group-containingcompound to be used herein can be selected from formamide, formic acid,and derivatives thereof, which are commercially available. Examples offormamide derivatives include nitrogen-substituted formamides such asN-methylformamide, N-ethylformamide, N-butylformamide,N,N-dimethylformamide, N,N-diethylformamide, N-methylformanilide, andN-ethylformanilide. Examples of formic acid derivatives include formicacid esters such as methyl formate, ethyl formate, propyl formate andbutyl formate, and formic acid salts such as sodium formate, potassiumformate, and ammonium formate.

Specific examples of the diamine represented by formula (VII) includestraight-chain or branched alkylenediamines such as ethylenediamine,1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane,hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane,1,9-diaminononane, 1,10-diaminodecane, 2,2,5-trimethylhexanediamine, and2,2,4-trimethylhexanediamine; alicyclic diamines such asisophoronediamine, 1,3-bis(aminomethyl)cyclohexane,bis(4-aminocyclohexyl)methane,bisaminomethylhexahydro-4,7-methaneindane, 1,4-cyclohexanediamine,1,3-cyclohexanediamine, 2-methylcyclohexanediamine,4-methylcyclohexanediamine, andbis(4-amino-3,5-dimethylcyclohexyl)methane, arylalkyldiamine such asm-xylylenediamine and p-xylylenediamine; aryldiamines such asp-phenylenediamine and 4,4'-diaminophenyl ether; andpolyoxyalkylenediamines such as polyoxypropylenediamine andpolyoxyethylenediamine. Particularly preferred among these diamines arealiphatic and alicyclic diamines.

Such a diamine may be in the form of either a partially neutralized salt(monosalt) or a completely neutralized salt (disalt). The diamine ispreferably in the form of a partially neutralized salt to give a highreaction efficiency.

The above-mentioned diamine is preferably used in the form of a saltobtained by partially neutralizing an acid. As such an acid there may bepreferably selected ones with an acid strength higher than carboxylicacids. Specific examples of such an acid include sulfuric acid; sulfonicacids such as benzenesulfonic acid, toluenesulfonic acid, andnaphthalenesulfonic acid; halogenic acids such as hydrochloric acid,hydrofluoric acid, hydrobromic acid, and hydroiodic acid; nitric acid;boric acid; and phosphoric acid. Preferred among these acids arehydrochloric acid and toluenesulfonic acid.

In the preparation of the above-mentioned diamine salt, theabove-mentioned diamine and the above-mentioned acid are used in a molarproportion, based on the total amount of amino groups in the diamine,corresponding to from 50 to 100% of the neutralization degree ascalculated in terms of acid equivalent. If this value falls below 50%,crosslinking and gelation are unavoidable during the imidizationreaction. On the contrary, if this value exceeds 100%, the imidizationreaction takes a prolonged period of time, giving an economicaldisadvantage. Thus, this value preferably ranges from 50 to 80%.

The diamine salt can be easily prepared by neutralization reaction ofthe corresponding diamine with the corresponding acid. For example, asalt obtained by adding a diamine dropwise to an alcohol solution of anacid may be concentrated as necessary, recrystallized from an alcohol,and then isolated to give a product which may be used as a startingmaterial. Alternatively, a diamine and an acid may be reacted with eachother in the above-mentioned formyl group-containing compound or anaprotic polar solvent such as 1,3-dimethyl-2-imidazolidinone (DMI),N-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), dimethylsulfone,dioxane, 1,2-dimethoxyethane, triamide hexamethylenephosphate, andtetramethylurea to form a partially neutralized salt which is then useddirectly in the reaction of the present invention. In the light of theoperational efficiency, the formyl group-containing compound ispreferably used to form a salt which is used then directly in thereaction of the present invention.

In the process (a) of the present invention, the reaction product thusobtained may be brought into contact with a base to undergodeacidification.

As another process for obtaining the copolymer of the present invention,there may be used the process (b) of the present invention, whichcomprises allowing the copolymer containing the above-mentionedrecurring units (A), (B) and (C') to undergo imidation or imidation andamidation simultaneously using as a reaction reagent a product obtainedby reacting a diamine represented by formula (VII) with theabove-mentioned formyl group-containing compound.

The reaction reagent can be prepared by allowing a diamine to imidationor amide exchange at a temperature of 60° C. to 180° C. preferably 80°C. to 150° C. for 2 to 5 hours in an amount of one mole or more,preferably from 1.5 to 5 mole per mole of the formyl group-containingcompound. In this reaction, if the formyl group-containing compound isformic acid, water is preferably distilled off. If the formylgroup-containing compound is a formic acid ester, the alcohol ispreferably distilled off. If the formyl group-containing compound is aformamide, the ammonia or amine is preferably distilled off. Theresulting product may be directly used for the subsequent imidationreaction or as an amidation reagent. However, the product usuallycontains unreacted diamines which can cause crosslinking and gelation.Therefore, the product is preferably heated under reduced pressure todistill off the unreacted diamines. Alternatively, if the unreacteddiamines are high-boiling point diamines, they are preferably onceneutralized with hydrochloric acid or the like and then subjected torecrystallization, whereby they are removed as a dihydrochloride.

The processes (a) and (b) of the present invention proceed as thecopolymer comprising the above-mentioned recurring units (A), (B) and(C') reacts with a salt of a diamine represented by formula (VII) and aformyl group-containing compound, or with a product obtained by reactinga diamine with a formyl group-containing compound. The imidationreaction may be effected in a state free of a solvent by means of ascrew extruder. However, for the purpose of avoiding local reaction andmaking the reaction homogeneous, an inert solvent is preferably usedbesides the formyl group-containing compound as a solvent. Examples ofinert solvents which can be used for such a purpose include aromatichydrocarbons such as benzene, toluene, xylene, cumene, cymene,ethyltoluene, propylbenzene, and diethylbenzene; alicyclic hydrocarbonssuch as methylcyclopentane, cyclohexane, ethylcyclopentane,methylcyclohexane, 1,1-dimethylcyclohexane, and ethylcylohexane;aliphatic hydrocarbons such as hexane, heptane, octane, decane,methylheptane, 3-ethylhexane, and trimethylpentane; and aprotic polarsolvents such as DMI, tetramethylurea, dimethylsulfone, dioxane,1,2-dimethoxyethane, triamide hexamethylenephosphate, DMSO, andN-methyl-2-pyrrolidone.

In accordance with the processes (a) and (b) of the present invention,reactive groups having significantly different polarities are reactedwith each other. In general, a nonpolar solvent and a polar solvent arepreferably used at the same time.

The amount of the above-mentioned solvent to be used is not specificallylimited but can be properly selected. In general, the amount of thesolvent to be used may be in the range of from 0.3 to 20 times,preferably from 1 to 10 times, the weight of the copolymer comprisingthe recurring units (A), (B) and (C') to be used as the startingmaterial (i.e., polyfunctional copolymer comprising a substituted orunsubstituted succinic anhydride as a funtional group). If this valuefalls below 0.3 time, the dilution effect is insufficient, giving ahighly thick reaction mixture that can cause some difficulties. On thecontrary, if this value exceeds 20 times, no improvements in the effectsof the solvent corresponding to the extra addition of the solvent can berecognized, giving economical disadvantages.

The proportion of the above-mentioned inert solvent to the formylgroup-containing compound (inert solvent/formyl group-containingcompound) is not specifically limited but is generally in the range offrom 40/60 to 100/0 by weight (100/0 corresponds to the process (b)),preferably from 50/50 to 95/5.

In the present invention, if as the substrate for imidation andamidation, there is used a product obtained by reacting a diamine with aformyl group-containing compound, the use of a formyl group-containingcompound as a solvent is not required. In the other case (i.e., process(a)), the use of a formyl group-containing compound is essential not asa solvent but as a reaction substrate. In this case, the formylgroup-containing compound is used in the form of a mixture with an inertsolvent to be used for dilution. The proportion of the formylgroup-containing compound is preferably increased depending on theproportion of the functional group in the starting material, to likelyprovide a higher solubility of the substrate and a higher reaction rate.

The imidation reaction and amidation reaction in the processes (a) and(b) of the present invention do not particularly require catalysts. Ifany used, a tertiary amine such as trimethylamine, triethylamine,tributylamine, N,N-dimethylaniline, N,N-diethylaniline, and1,8-diazabicyclo(5.4.0)undecene-7 is suitable.

In the present invention, the proportion of the copolymer, the diamineor salt thereof, and the formyl group-containing compound used asstarting materials depends on the kind and conditions of the startingmaterials used and thus cannot be unequivocally determined but isnormally in the range of from 1.0 to 10 mole, preferably from 1.05 to5.0 mole, per mole of the substituted or unsubstituted succinicanhydride group (i.e., recurring unit (C')) contained in the startingcopolymer based on the amount of the unneutralized or unreacted aminogroup in the diamine. If this value falls below 1.0 mole, some succinicanhydride groups are left unimidated or unamidated after the completionof the reaction. In the process (a) of the present invention, a primaryamino group regenerated in the deacidification process reacts with thesuccinic anhydride groups to give amide crosslinkage that causesgelation, eliminating the effects of the present invention. On thecontrary, if this value exceeds 10 mole, the imidation or amidationadvantageously proceeds rapidly but causes an ecomical disadvantagerequiring a large amount of a reaction reagent.

In the processes (a) and (b) of the present invention, the reactiontemperature and reaction time depend on the kind of the solvent used andthe presence of catalyst but are normally in the range of from 100° C.to 250° C., preferably from 110° C. to 200° C., and from 1 to 20 hours,respectively. If the reaction temperature falls below 100° C., it isdisadvantageous in that the reaction requires a prolonged period oftime. On the contrary, if the reaction temperature exceeds 250° C., thereaction product is likely colored, and the formamide group thusincorporated likely undergoes thermal decomposition.

Therefore, if the above-mentioned reaction is effected in a state freeof a catalyst or at a relatively low temperature, or with a reactionreagent in a small molar proportion to the starting material, theproduction yield of the recurring units (C) and (D) are high while thatof the recurring unit (E) is so small as to be substantially neglected.

On the other hand, if the above-mentioned reaction is effected in thepresence of the above-mentioned catalyst or at an elevated temperature,or with a reaction reagent in a large molar proportion to the startingmaterial, the production yield of the recurring unit (E) increases.

Concerning the proportion of the formamide group to the amino group, ifas the imidation or amidation reagent there is used a reaction productbetween a diamine and a formyl group-containing compound, a copolymercomprising a formamide group in an amount of substantially 100% can beobtained. Further, if a diamine salt is used, a copolymer comprising amixture of a formamide group and an amino group is obtained. In thiscase, the higher the reaction temperature is, or the longer the reactiontime is, the higher is the production yield of the formamide group.

Thus, under the above-mentioned reaction conditions, a copolymer can beobtained with a (recurring unit (C)+recurring unit (D))/recurring unit(E) proportion of from 100/0 to 30/70 and a formamide group/amino groupproportion of from 100/0 to 30/70.

The formulations of the copolymer of the present invention can bedetermined by the peak intensity ratio of carbonyl carbon (W) in theimide ring, carbonyl carbon (Y) in the amide and carbonyl carbon (Z) inthe formamide group appearing in the vicinity of 176 to 180 ppm, 172 to174 ppm and 162 ppm, respectively, in a chemical shift obtained bymeasuring nuclear magnetic resonance (¹³ C-NMR) using isotope carbon.

In the process (a) of the present invention, the order of charging thestarting materials is not specifically limited but can be widelyselected. In general, to the formyl group-containing compound (or asolution thereof in another solvent) may be added a salt of theabove-mentioned diamine with an acid in the form of a powder or solutionto make a solution to which the copolymer comprising the recurring units(A), (B) and (C') is then gradually added. This order of charging may bereversed. During this process, the charging of the materials may beeffected while the solvent (or formyl group-containing compound) isheated under reflux.

Also in the process (b) of the present invention, the order of chargingthe starting materials is not specifically limited but can be widelyselected. In general, the copolymer comprising the recurring units (A),(B) and (C') may be uniformly dissolved in a solvent to make a solutionto which a product obtained by reacting the above-mentioned diamine withthe formyl group-containing compound is then gradually added. This orderof charging may be reversed. During this process, the charging of thematerials may be effected while the solvent is heated under reflux.

Since imidation or amidation reaction of the starting copolymer with adiamine salt and a formyl group-containing compound, or with a productobtained by reacting a diamine with a formyl group-containing compoundproceeds with the production of water, the water produced azeotropicallyboils together with the solvent used. By removing the azeotropicallyboiled water from the reaction system by means of a Dean-Stark waterseparator or the like, the reaction can proceed efficiently.

The completion of the imidation or amidation reaction can be confirmedby recognizing that the water azeotrope no longer occurs or that theinfrared absorption spectrum of a specimen sampled from the reactionmixture no longer shows an increase in the absorption intensity ofcarbonyl in the imide in the vicinity of 1,700 cm⁻¹.

The reaction mixture contains a salt of the copolymer of the presentinvention to which a formamide group or a formamide group and a primaryamino group are bonded via an imide bond or an imide bond and an amidebond. This reaction mixture may be, directly or optionally in the formof a powder obtained by charging it in a nonsolvent such as methanol,isopropanol, isobutanol, hexane and water, brought into contact with anaqueous solution of a base or optionally a solution of the base in amixture of methanol and water to undergo deacidification to convert itinto a free amine. Specific examples of such a base to be used in thedeacidification include water-soluble bases such as sodium hydroxide,potassium hydroxide, lithium hydroxide, sodium carbonate, potassiumcarbonate, sodium bicarbonate, potassium bicarbonate, ammonia,methylamine, ethylamine, trimethylamine, and triethylamine. Preferredamong these bases are sodium hydroxide, sodium carbonate, and sodiumbicarbonate for economic reasons. In accordance with the process (b) ofthe present invention, no salt of the copolymer is produced, requiringno such a deacidification process.

The purification of a copolymer comprising a formamide group alone canbe easily accomplished by charging the reaction product thus obtained inthe above-mentioned nonsolvent such as methanol, isopropanol,isobutanol, hexane, and water, and then recovering the resultingprecipitate in the form of a powder.

The process for the conversion of the formamide group in the copolymerthus obtained into a primary amino group is not specifically limited butmay be selected from known processes. For example, the copolymercontaining a formamide group may be treated in the form of a solution ina proper solvent or a dispersion with an aqueous solution of a mineralacid such as hydrochloric acid and hydrofluoric acid, or may behydrolyzed to convert the formamide group into a salt of thecorresponding primary amine. Preferably, the copolymer may be hydrolyzedunder acidic conditions as in the process (c) of the present invention.

In the process (c), the acidic conditions are not specifically limited.In general, the pH value is preferably in the range of 3 or less. Thehydrolysis is preferably effected with a mineral acid such ashydrochloric acid and sulfuric acid.

The primary amine salt thus obtained can be optionally converted into afree primary amine by the same method as mentioned above.

In the present invention, it can be presumed that when a partiallyneutralized salt of diamine or a product obtained by reacting a diaminewith a formyl group-containing compound, i.e., a partial formamide ofdiamine, is used as an imidation reagent in the presence of a formylgroup-containing compound, the reactivity of one end of the diamine issuppressed while the primary amine at the other end selectivelycontributes to the imidation or amidation reaction, making it possibleto smoothly obtain the desired copolymer without causing anycrosslinking. Even in the case where a partially neutralized salt ofdiamine is used, a formamide group is contained in the reaction product.This is probably because the diamine salt undergoes an amide exchangereaction with the formyl group-containing compound used as a solventduring the reaction.

In the present invention, the formamide group thus produced serves as aprimary amine protective group which can inhibit side reactions duringthe imidation reaction at an elevated temperature, making it possible toobtain a copolymer with a good hue.

The formamide group-containing copolymer thus obtained can be optionallyconverted into an amino group. Alternatively, if the copolymer is usedas a polymer compatibilizer, a resin modifier, or the like, it canundergo thermal decomposition to become a more active functional group.

The copolymer of the present invention can be melt-kneaded with athermoplastic resin such as engineering plastics and an olefinic polymerand/or a styrenic polymer to obtain a resin composition which exhibitsexcellent impact properties (particularly face impact properties) andexternal appearance and reduced coloring and undergoes no peeling.

That is, the present invention further provides a thermoplastic resincomposition comprising as main components 100 parts by weight of amixture of (i) from 5 to 95% by weight of a thermoplastic resincontaining a functional group capable of reacting with an amino groupand (ii) from 95 to 5% by weight of an olefinic polymer and/or astyrenic polymer; and (iii) from 0.05 to 20 parts by weight of theabove-mentioned copolymer or a salt thereof.

The composition of the present invention comprises the components (i),(ii) and (iii) as mentioned above. The component (i) may contain afunctional group capable of reacting with an amino group. In otherwords, it can be considered that the formamide group contained in thecomponent (iii) undergoes a carbon monoxide removal reaction by the heatgenerated during the melt kneading to convert the copolymer containingthe formamide into a copolymer containing an amino group. Therefore, anycompound containing a functional group capable of reacting with an aminogroup which is considered to be produced from the component (iii) can beused as the component (i). It can be further considered that during themelt-kneading the component (iii) is converted into an amino group witha high reactivity which then rapidly reacts with the component (i),making it difficult to cause side reactions such as coloring. It cantherefore be considered that this process causes reduced coloring ascompared to the case where a (polymer) reagent containing an amino groupis used during the melt-kneading.

Specific examples of the functional group capable of reacting with anamino group include groups consisting of carboxylic acids, other organicacids, esters and salts thereof, acid anhydrides, salts thereof,hydroxyl groups, thiol, oxazoline groups, epoxy groups, isocyanategroups, amide bond, carbonate bond, urethane bond, urea bond, and etherbond. As the component (i) there may be preferably used a thermoplasticresin containing at least one bond selected from carbonate bond, esterbond, amide bond and ether bond.

Typical examples of the thermoplastic resin containing a carbonate bondto be used as the component (i) include polycarbonate resins which maybe aliphatic or aromatic. The molecular weight of these polycarbonateresins is not specifically limited but is normally in the range of from10,000 to 100,000, preferably from 10,000 to 40,000 as calculated interms of number-average molecular weight in the light of the moldabilityand physical properties of the resulting composition. Thesepolycarbonate resins may be terminated by a usual monovalent phenolgroup (e.g., phenol, halogen-substituted phenol, alkyl-substitutedphenol such as cumylphenol and octylphenol, other various substitutedphenols). Alternatively, these polycarbonate resins may contain theabove-mentioned functional group or bond capable of reacting with anamino group in the form of a graft, block or random copolymer, or may beterminated by the above-mentioned functional group or bond. Further, forthe purpose of modification or reinforcement, these polycarbonate resinsmay further comprise elastomers, fillers or other various additivesincorporated therein during or after polymerization.

These polycarbonate resins can be prepared by various known methods suchas a phosgene method, an ester interchange method and a meltpolymerization method.

There are various kinds of the above-mentioned polycarbonate resins suchas those containing a recurring unit represented by formula (VIII):##STR6## wherein Z represents a mere bond or an alkylene groupcontaining from 1 to 8 carbon atoms, an alkylidene group containing from2 to 8 carbon atoms, a cycloalkylene group containing from 5 to 15carbon atoms, a cycloalkylidene group containing from 5 to 15 carbonatoms, SO₂, SO, O, CO, or a group represented by the following formula:##STR7## Y represents a hydrogen atom, a chlorine atom, a bromine atom,or a saturated alkyl group containing from 1 to 8 carbon atoms; and aand b each represents an integer of from 0 to 4.

The preparation of such a polycarbonate resin can be accomplished by thesolvent process, i.e., a reaction with a divalent phenol and a carbonateprecursor such as phosgene in the presence of a known acid acceptor anda molecular weight adjustor in a solvent such as methylene chloride, oran ester interchange reaction with a divalent phenol and a carbonateprecursor such as diphenyl carbonate.

Examples of divalent phenols which can be preferably used includebisphenols. In particular, 2,2-bis(4-hydroxyphenyl)propane (commonlyreferred to as "bisphenol A") is preferred. Further, compounds obtainedby partially or entirely substituting bisphenol A by other divalentphenol. Examples of divalent phenols other than bisphenol A includecompounds such as hydroquinone, 4,4'-dihydroxydiphenyl,bis(4-hydroxyphenyl)alkanes, bis(4-hydroxyphenyl)cycloalkanes,bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone,bis(4-hydroxyphenyl)sulfoxide, and bis(4-hydroxyphenyl)ether; andhalogenated bisphenols such as bis(3,5-dibromo-4-hydroxyphenyl)propaneand bis(3,5-dichloro-4-hydroxyphenyl)propane. Such divalent phenols maybe a homopolymer or two or more kinds of copolymers of divalent phenols,or a blend thereof. Further, such a polycarbonate resin may be athermoplastic random-branched polycarbonate obtained by reacting apolyfunctional aromatic compound with a divalent phenol and/or acarbonate precursor.

Examples of thermoplastic resins containing a carbonate bond other thanthe above-mentioned polycarbonate resins include polyarylate resins andpolyester polycarbonate resins, and these resins can be preferably usedin the present invention.

As the resin used as the component (i), thermoplastic resins containingan ester bond, i.e., polyester resins, can be used in addition to theresins containing a carbonate bond. The kind of the polyester resin isnot specifically limited but can be selected from many varieties. Thepolyester resin may be either aliphatic or aromatic. In the light ofphysical properties, the latter polyester resin is preferred. Themolecular weight of the polyester resin can be properly selecteddepending on the purpose but is normally in the range of from 0.2 to 2.0dl/g, preferably from 0.5 to 1.2 dl/g in terms of intrinsic viscosity.The polyester resin may be terminated by a carboxylic acid or alcoholichydroxyl group. The proportion of such a terminal group is notspecifically limited but is preferably in the range of from 9/1 to 1/9.Alternatively, the polyester resin may contain the above-mentionedfunctional group or bond capable of reacting with an amino group in theform of a graft, block or random copolymer, or may be terminated by theabove-mentioned functional group or bond. Further, for the purpose ofmodification or reinforcement, the polyester resin may further compriseelastomers, fillers or other various additives incorporatedtherein-during or after polymerization. Moreover, the polyester resinmay contain two or more kinds of dicarboxylic acids so far as thephysical properties thereof are not impaired.

Such a polyester resin can be prepared by various known methods. Thereare many varieties of such a polyester resin.

Specific examples of the polyester resin which can be used in thepresent invention include polyethylene terephthalate (PET), polybutyleneterephthalate (PBT), polycyclohexadimethylene terephthalate (PCT), andpolyarylates. Particularly preferred among these polyester resins ispolyethylene terephthalate. Such polyethylene terephthalate may be apolyester consisting of an aromatic dicarboxylic acid component mainlycomprising terepthalic acid and a glycol component mainly comprisingethylene glycol, or a polyester obtained by copolymerization of otherdicarboxylic acid component and glycol component.

As the resin to be used as the component (i) there can be used athermoplastic resin containing an amide bond, i.e., a polyamide resin.The kind of the polyamide resin is not specifically limited but can beselected from many varieties. The polyamide resin may be eitheraliphatic or aromatic. The molecular weight of the polyamide resin isnot specifically limited but is normally in the range of from 4,000 to50,000, preferably from 5,000 to 30,000 as calculated in terms ofnumber-average molecular weight in the light of the moldability andphysical properties of the resulting composition. Alternatively, thepolyamide resin may contain the above-mentioned functional group or bondcapable of reacting with an amino group in the form of a graft, block orrandom copolymer, or may be terminated by the above-mentioned functionalgroup or bond. Further, for the purpose of modification orreinforcement, the polyamide resin may further comprise elastomers,fillers or other various additives incorporated therein during or afterpolymerization.

Such a polyamide resin can be prepared by various known methods such asring opening (co)polymerization or (co)polycondensation of a 3-memberedor more cyclic lactam or a polymerizable ω-amino acid or dibasic acidwith a diamine. More particularly, such a polyamide resin can beprepared by (co)polymerization of ε-caprolactam, aminocaproic acid,11-aminoundecanoic acid, etc., or (co)polycondensation of a diamine suchas hexamethylenediamine, nonamethylenediamine, undecamethylenediamine,dodecamethylenediamine and metaxylylenediamine with a dicarboxylic acidsuch as terepthalic acid, isophthalic acid, adipic acid, sebasic acid,dibasic dodecanoic acid, and glutaric acid.

As such a polyamide resin there can be selected from many varieties.Specific examples of such a polyamide resin include aliphatic polyamidessuch as nylon 6 (polyamide 6), nylon 6,6, nylon 6,10, nylon 11, nylon12, nylon 6,12, and nylon 4,6; aliphatic copolymeric polyamides such asnylon 6/6,6, nylon 6/6,10, and nylon 6/6,12; and aromatic polyamidessuch as polyhexamethylenediamine terephthalimide,polyhexamethylenediamine isophthalamide and xylene group-containingpolyamides (e.g., nylon-MXD (methaxylylenediamine)). Further examples ofsuch a polyamide resin include polyester amides, polyether amides andpolyester-ether amides. Particularly preferred among these polyamideresins are nylon 6 and nylon 6,6.

As the resin to be used as the component (i) there can be further used athermoplastic resin containing an ether bond, i.e., a polyether resin.The kind of the polyether resin is not specifically limited but can beselected from many varieties. The polyether resin may be eitheraliphatic or aromatic. Alternatively, the polyamide resin may containthe above-mentioned functional group or bond capable of reacting with anamino group in the form of a graft, block or random copolymer, or may beterminated by the above-mentioned functional group or bond.

There are many varieties of such a polyether resin. These polyetherresins can be roughly divided into some groups: polyacetal homopolymerssuch as polyoxymethylene (POM); polyacetal copolymers comprising amixture of polyether unti components, such as a trioxane-ethylene oxidecopolymer; polyphenylene ether (PPE); polyether sulfone (PES) comprisinga mixture of an ether group and a sulfone group; polyether ketone (PEK)comprising a mixture of an ether group and a carbonyl group;polyphenylene sulfide (PPS) containing a thioether group; andpolysulfone (PSO). Preferred among these polyether resins arepolyacetals (polyoxymethylene (POM)) and polyphenylene ether (PPE).

The above-mentioned polyacetal homopolymer is a polymer containing anoxymethylene unit as a main molecular chain and can be prepared byhomopolymerization of formaldehyde or trioxane. On the other hand, theabove-mentioned polyacetal copolymer is a copolymer comprising anoxyalkylene unit such as an oxyethylene unit, an oxypropylene unit andan oxytetramethylene unit, or an oxyphenylethylene unit mixed in a chainconsisting of the above-mentioned oxymethylene unit. Such a polyacetalcopolymer can be prepared by copolymerization of formaldehyde ortrioxane with a cylic ether such as ethylene oxide.

In the composition of the present invention, as the component (i) therecan be used one or a mixture of two or more kinds of the above-mentionedresins. On the other hand, as the component (ii) there can be used anolefinic polymer, a styrenic polymer, or a mixture thereof. The kind ofthe olefinic polymer is not specifically limited, but any resincontaining a polyolefin component can be used. Many varieties of such anolefinic polymer can be used. Specific examples of such a polyolefinicresin include polyethylene (such as linear low-density polyethylene(LLDPE), low-density polyethylene (LDPE), very low-density polyethylene(VLDPE) and high-density polyethylene (HDPE)), polypropylene,polybutene, polyisobutene, ethylene-α-olefin copolymers (such as anethylene-propylene copolymer, an ethylene-propylene copolymer rubber(EPR), an ethylene-butene copolymer (EBM), an ethylene-propylene-dienecopolymer (EPDM), an ethylene-propylene-butene copolymer, and anethylene-butylene copolymer), copolymers of propylene with otherα-olefins (such as a propylenebutene copolymer), various ethyleniccopolymers (such as an ethylene-vinyl acetate copolymer (EVA), anethylene-vinyl alcohol copolymer (EVOH), an ethylene-maleic anhydridecopolymer, and an ethylene-alkyl (meth)acrylate copolymer),poly(4-methyl-1-pentene), and mixtures thereof. These copolymers includerandom, block, random block and graft copolymers.

The molecular weight of the above-mentioned olefinic polymers can beproperly selected depending on various conditions but is normally in therange of from 5,000 to 300,000, preferably-from 10,000 to 200,000 ascalculated in terms of number-average molecular weight.

As the styrenic polymer to be used as the component (ii) there may beused any compound containing a styrene component such as styrene,α-methylstyrene, and p-methylstyrene. The kind of such a styrenicpolymer is not specifically limited. Examples of such a styrenic polymerinclude general-purpose polystyrene (GPPS), high-impact polystyrene(HIPS), syndiotactic polystyrene (SPS), a styrene-maleic acid copolymer(SMA), a styrene-maleimide copolymer, rubber-reinforced SMA, an MSresin, an AS resin, and an ABS resin (including a high-heat resistanceABS resin, an AAS resin, an AES resin, etc.). Further examples of such astyrenic polymer include so-called styrenic thermoplastic elastomerssuch as an SEBS resin, an SEPS resin, an SEP resin, and derivativesthereof.

The molecular weight of the above-mentioned styrenic polymer can beproperly selected depending on various conditions but is normally in therange of from 20,000 to 300,000, preferably from 30,000 to 200,000 ascalculated in terms of number-average molecular weight.

In the composition of the present invention, the proportion of thecomponent (i) to the component (ii) is in the range of from 5:95 to95:5, preferably from 30:70 to 95:5 (by weight). If the mixingproportion of the components (i) and (ii) deviates from theabove-specified range, it causes some disadvantages. If the mixingproportion of the component (i) exceeds the above-specified range, themoldability of the composition is deteriorated. On the other hand, themixing proportion of the component (ii) exceeds the above-specifiedrange, the resulting composition suffers from insufficiency ofmechanical strengths such as rigidity.

The mixing proportion of the component (iii) based on a total of 100parts by weight of the components (i) and (ii) is in the range of from0.05 to 20 parts by weight, preferably from 0.5 to 10 parts by weight.If the mixing proportion of the component (iii) falls below 0.05 part byweight, the resulting composition leaves much to be desired in variousphysical properties such as face impact strength. On the contrary, ifthe mixing proportion of the component (iii) exceeds 20 parts by weight,there can be recognized no improvements in the effects of the presentinvention corresponding to the extra addition, giving economicaldisadvantages and ill-balancing the physical properties of the resincomposition.

The resin composition of the present invention comprises the components(i), (ii) and (iii) and may further comprise other additives (e.g.,reinforcements such as glass fibers and carbon fibers, inorganicfillers, thermal stabilizers, antioxidants, photo-stabilizers, fireretardants, weathering agents, plasticizers, antistatic agents, releaseagents, foaming agents) incorporated therein as necessary.

In the preparation of the resin composition of the present invention,these components may be melt-kneaded at an elevated temperature by meansof a kneader such as a single-screw extruder, a twin-screw extruder, aBanbury mixer, a kneading roll, a Brabender, and a kneader, or a mixersuch as a Henshel mixer. In this process, the order of kneading is notspecifically limited but can be properly selected. The kneadingtemperature depends on the kind and blended amount of components usedand the desired physical properties of the composition to be preparedand cannot be unequivocally determined but is normally in the range offrom 180° to 340° C.

The preparation of the resin composition of the present invention can beaccomplished by kneading a proper combination of the components (i),(ii) and (iii). Taking into account the compatibility among thesecomponents, for example, if the component (ii) is an olefinic polymer,the component (iii) is preferably an olefinic formamide group-containingcompound (e.g., a compound obtained by incorporating a formamide groupin an ethylene-ethyl acrylate-maleic anhydride copolymer). Further, ifthe component (ii) is a styrenic polymer, the component (iii) ispreferably a styrenic formamide group-containing compound (e.g., acompound obtained by incorporating a formamide group in a styrene-maleicanhydride copolymer).

The present invention will be further described in the followingexamples but the present invention should not be construed as beinglimited thereto.

REFERENCE EXAMPLE 1 (Preparation of partially neutralized salt ofethylenediamine with p-toluenesulfonic acid)

In a 1-l capacity flask equipped with a thermometer, a stirrer, adropping funnel and a reflex condenser were charged 300 ml of methanoland 95 g (0.5 mole) of p-toluenesulfonic acid monohydrate to make asolution.

To the solution was added dropwise a solution of 150 g (2.5 mole) ofethylenediamine in 300 ml with cooling in an ice bath at a rate suchthat the temperature was kept at 10° C. to 20° C. After completion ofthe dropwise addition, the mixture was heated to a temperature of 70° C.The methanol and unreacted ethylenediamine were then distilled off underreduced pressure. As a result, 132.7 g of a white solid was deposited.

The white solid thus obtained was recovered and filtered into a slurrywith 300 ml of toluene. The slurry was washed with 100 ml of toluenetwice to obtain a white powder which was then dried under reducedpressure. The yield was 109.8 g.

The white powder was titrated with 0.5N hydrochloric acid withbromophenol blue being used as an indicator to determine theneutralization equivalent and neutralization degree. The results are setforth in Table 1.

REFERENCE EXAMPLE 2 (Preparation of partially neutralized salt ofethylenediamine with hydrochloric acid)

A monohydrochloride of ethylenediamine was prepared in the form of awhite powder in the same manner as in Reference Example 1 using the samereaction vessel as used in Reference Example 1, except that a 35%aqueous solution of hydrochloric acid was used instead of thep-toluenesulfonic acid. The neutralization equivalent and neutralizationdegree determined in the same manner as in Reference Example 1 are setforth in Table 1.

REFERENCE EXAMPLE 3 (Preparation of partially neutralized salt ofhexamethylenediamine with p-toluenesulfonic acid)

95 g (0.5 mole) of p-toluenesulfonic acid monohydrate was dissolved in500 ml of dimethylformamide (DMF) in the same reaction vessel as used inReference Example 1 at room temperature. 52.2 g (0.45 mole) ofhexamethylenediamine was gradually added to and dissolved in thesolution in such a manner that the temperature of the solution did notexceed 20° C. to prepare a DMF solution of a partially neutralized saltof hexamethylenediamine with p-toluenesulfonic acid. The neutralizationequivalent and neutralization degree per solid content determined in thesame manner as in Reference Example 1 are set forth in Table 1.

REFERENCE EXAMPLES 4 & 5

A salt of a diamine with an acid was prepared in the same manner as inReference Example 3, except that the kinds of the diamine and acid usedwere altered as shown in Table 1. The neutralization equivalent andneutralization degree of the salt per solid content are set forth inTable 1.

                                      TABLE 1                                     __________________________________________________________________________                                 Concentra-                                                                    tion of                                                                              Neutrali-                                                                             Neutrali-                                                      solid content                                                                        zation  zation                                                    Solvent                                                                            of salt                                                                              equivalent                                                                            degree                            Diamine        Acid     used (%)    (eq/g)  (%)                               __________________________________________________________________________    Reference                                                                           Ethylenediamine                                                                        p-Toluenesulfonic                                                                      None 100    4.21 × 10.sup.-3                                                                50.7                              Example 1      acid                                                           Reference                                                                           Ethylenediamine                                                                        Hydrochloric acid                                                                      None 100    10.15 × 10.sup.-3                                                               50.7                              Example 2                                                                     Reference                                                                           Helxamethylene-                                                                        p-Toluenesulfonic                                                                      DMF  20.5   2.81 × 10.sup.-3                                                                56.4                              Example 3                                                                           diamine  acid                                                           Reference                                                                           1,3-Bis(amino-                                                                         p-Toluenesulfonic                                                                      DMF  20.0   2.90 × 10.sup.-3                                                                53.0                              Example 4                                                                           methyl)cyclo-                                                                          acid                                                                 hexanediamine                                                           Reference                                                                           m-Xylylene-                                                                            p-Toluenesulfonic                                                                      Form-                                                                              25.0   2.35 × 10.sup.-3                                                                59.1                              Example 5                                                                           diamine  acid     amide                                                 __________________________________________________________________________

REFERENCE EXAMPLE 6 (Preparation of reaction product of ethylenediaminewith formamide)

45 g (1.0 mole) of formamide was gradually added dropwise to 300 g (5.0mole) of ethylenediamine at room temperature in the same reaction vesselas used in Reference Example 1. The reaction system was then allowed toundergo a reaction at an elevated temperature of 80° C. to 120° C. for 5hours. During this process, the evolution of ammonia gas was recognized.

After completion of the reaction, the unreacted ethylenediamine wasdistilled off at a temperature of 61° C. under a pressure of 88 mmHg toobtain a residue. The results determined by the neutralization titrationof the residue are set forth in Table 2.

REFERENCE EXAMPLE 7 (Preparation of reaction-product ofhexamethylenediamine with DMF)

DMF was added dropwise to hexamethylenediamine to effect the reaction inthe same manner as in Reference Example 6. The reaction mixture wasdissolved in a solvent (7:3 (volumetric ratio) mixture of ethanol andwater), neutralized with 35% hydrochloric acid, and then concentrated,followed by recrystallization. The resulting hydrochloride ofhexamethylenediamine in a needle crystal form was removed by filtration.The results determined by the potentiometric titration of theconcentrated residue are set forth in Table 2.

REFERENCE EXAMPLE 8 (Preparation of reaction product of1,3-bis(aminomethyl)-cyclohexanediamine with DMF)

DMF was added dropwise to 1,3-bis(aminomethyl)-cyclohexanediamine toeffect the reaction in the same manner as in Reference Example 7. Thereaction mixture was filtered. The results determined by thepotentiometric titration of the concentrated residue are set forth inTable 2.

REFERENCE EXAMPLE 9 (Preparation of reaction product ofm-xylylenediamine with formic acid )

272 g (2.0 mole) of m-xylenediamine and 23 g (0.5 mole) of formic acidwere-allowed to undergo a reaction at a temperature of 120° C. for 10hours while water was distilled off in a Dean-Stark water separator. Theresulting product was treated in the same manner as in Reference Example7 to obtain the desired reaction product. The results of potentiometrictitration are set forth in Table 2.

                  TABLE 2                                                         ______________________________________                                                                      Neutral-                                                            Formyl    ization                                                             group-    equivalent                                      Diamine             compound  (eq/g)                                          ______________________________________                                        Reference                                                                             Ethylenediamine Formamide 10.79 × 10.sup.-3                     Example 6                                                                     Reference                                                                             Hexamethylenediamine                                                                          DMF        6.25 × 10.sup.-3                     Example 7                                                                     Reference                                                                             1,3-Bis(aminomethyl)-                                                                         DMF        5.11 × 10.sup.-3                     Example 8                                                                             cyclohexanediamine                                                    Reference                                                                             m-Xylylene      Formic     5.50 × 10.sup.-3                     Example 9               acid                                                  ______________________________________                                    

EXAMPLE 1

In a 1-l capacity flask equipped with a thermometer, a stirrer, adropping funnel and a Dean-Stark water separator were charged 300 ml ofDMF and 18.2 g of ethylenediamine p-toluenesulfonate. The mixture washeated to a temperature of 80° C. to make a solution.

A solution of 100 g of a styrene-maleic anhydride (molar ratio: 95/5 )copolymer (NMP-1) (weight-average molecular weight (Mw): 52,000;number-average molecular weight (Mn): 25,000) in 400 ml of xylene wasadded dropwise to the solution through the dropping funnel.

After completion of the dropwise addition, the reaction mixture waspartially recovered and measured for infrared absorption spectra. As aresult, the absorption due to the anhydrous ring at a wavelength of1,780 cm⁻¹ completely disappeared.

As the reaction system was kept heated up to near 140° C. the reflux ofxylene was accompanied by the azetropy of water which was then separatedthrough the Dean-Stark water separator.

The reaction was continued at a temperature of 140° C. for 15 hours.When the production of water was no longer recognized, the reaction wasstopped. The reaction mixture was then charged in 5 l of methanol. Theproduct was recovered as a precipitate.

A part of the precipitate was dissolved in toluene. A cast film was thenprepared from this solution. The cast film was measured for infraredabsorption spectra. There were observed an absorption due to the imidering at 1,768 cm⁻¹ and 1,697 cm⁻¹, an absorption due to the foramidegroup at 1,664 cm⁻¹ (shoulder) and 1,530 cm⁻¹, and an absorption due top-toluenesulfonic acid, which was not observed in the styrene-maleicanhydride copolymer as the starting material, at 1,100 cm⁻¹ and 580cm⁻¹. It was thus confirmed that a formamide group and a primary aminogroup were bonded to a polystyrene via an imide bond in the form ofp-toluenesulfonate.

The precipitate thus obtained was dipped in a solution of 7.0 g ofpotassium carbonate in a 1:1 (volumetric ratio) mixture of water andmethanol overnight, filtered off, thoroughly washed with water andmethanol, and then dried. The yield was 101.5 g.

The copolymer (FAP-1) thus obtained was a white powder soluble intoluene. The copolymer was then dissolved in toluene in a proportion of10% by weight and measured for viscosity by means of a B type viscometerat a temperature of 25° C. The result was 650 cps. A toluene cast filmwas prepared from this solution. The cast film was then measured forinfrared absorption spectra. There were obserbed an absorption by theimide ring at 1,768 cm⁻¹ and 1,697 cm⁻¹ and an absorption by theformamide group at 1,664 cm⁻¹ (shoulder) and 1,530 cm⁻¹. The absorptiondue to p-toluenesulfonic acid at 1,100 cm⁻¹ and 580 cm⁻ disappeared.Further, there was observed an absorption due to the amino group at3,434 cm⁻¹.

On the other hand, nuclear magnetic resonance spectra (¹³ C-NMR)measured with isotope carbon in CDCl₃ showed a peak corresponding tocarbonyl carbon in the imide ring with an intensity ratio of 2.00 at 176to 180 ppm and a peak corresponding to carbonyl carbon in the formamidegroup with an intensity ratio of 0.891 at 162 ppm but no peak indicatingthe presence of carbonyl carbon in the amide group at 172 to 174 ppm.

From the results of NMR spectra, the functional group proportions (molarproportion) ((III)+(IV))/(V) and --NH--CHO group/NH₂ group weredetermined to be 100/0 and 89/11, respectively.

EXAMPLE 2

In the same reaction vessel as used in Example 1 were charged 200 ml ofDMF and 83.0 g of ethylenediamine hydrochloride. The mixture was heatedto a temperature of 70° C. to make a solution. A solution of 100 g of anisobutyrene-maleic anhydride copolymer (NMP-2) (molar proportion: 50/50)(Mw: 9,000; Mn: 4,100) in 300 ml of a 1:1 (volumetric ratio) mixture ofxylene and DMF was gradually added dropwise to the solution thusobtained.

The reaction solution was then heated to a temperature of 140° C. wherethe reaction was allowed to continue for 8 hours while water was removedby azeotropy. The reaction mixture was concentrated to 400 ml underreduced pressure. The concentrate thus obtained was charged in 5 l ofisopropanol. The resulting precipitate was dipped in 1,000 ml of asolution of 106 g of sodium carbonate in a 1:1 (volumetric ratio)mixture of water and isopropanol overnight, filtered off, thoroughlywashed with water and isopropanol, and then dried. The yield was 137.8g.

The copolymer thus obtained was a white powder which was then dissolvedin a 1:1 (volumetric ratio) mixture of xylene and DMI in a proportion of10% by weight. The solution was then measured for viscosity at atemperature of 25° C. The result was 45 cps.

The infrared absorption spectra (KBr tablet method) of the copolymerthus obtained (FAP-2) showed an absorption by the imide ring at 1,770cm⁻¹ and 1,695 cm⁻¹, an absorption by the formamide group at 1,655 cm⁻¹(shoulder) and 1,527 cm⁻¹, and an absorption by the amino group at 3,434cm⁻¹.

On the other hand, nuclear magnetic resonance spectra (¹³ C-NMR)measured in DMSO-⁶ d showed a peak corresponding to carbonyl carbon inthe imide ring with an intensity ratio of 2.00 at 176 to 180 ppm and apeak corresponding to carbonyl carbon in the formamide group with anintensity ratio of 0.643 at 162 ppm but no peak indicating the presenceof carbonyl carbon in the amide group at 172 to 174 ppm.

From the results of NMR spectra, the functional group proportions (molarproportion) ((III)+(IV))/(V) and --NH--CHO group/NH₂ group weredetermined to be 100/0 and 64.3/35.7, respectively.

EXAMPLE 3

In the same reaction vessel as used in Example 1 were charged 120 g of astyrene-isoprene-maleic anhydride (molar proportion: 48/48/4) copolymer(NMP-3) (Mw: 40,000; Mn: 18,000) and 500 ml of xylene to make asolution. The solution thus obtained was heated to a temperature of 140°C. where a solution of 17.8 g of a reaction product ofhexamethylenediamine with DMF as prepared in Reference Example 7 wasadded thereto under reflux of xylene.

The reaction was allowed to continue at a temperature of 140° C. for 5hours while water produced by azeotropy was continuously removed throughthe Dean-Stark water separator.

After completion of the reaction, the reaction mixture was cooled andthen charged in 5 l of methanol. The product was then recovered as aprecipitate.

The precipitate was washed with methanol and dried to obtain 123.2 g ofa desired copolymer (FAP-3).

The copolymer thus obtained was a pale yellowish white powder soluble intoluene. The copolymer was dissolved in toluene in a proportion of 10%by weight and measured for viscosity by means of a B type viscometer ata temperature of 25° C. The result was 780 cps. A toluene cast film wasprepared from this solution. The cast film was then measured forinfrared absorption spectra. There were observed an absorption by theimide ring at 1,770 cm⁻¹ and 1,702 cm⁻¹ and an absorption by theformamide group at 1,660 cm⁻¹ (shoulder) and 1,531 cm⁻¹.

On the other hand, nuclear magnetic resonance spectra (¹³ C-NMR)measured in CDCl₃ showed a peak corresponding to carbonyl carbon in theimide ring with an intensity ratio of 2.00 at 176 to 180 ppm and a peakcorresponding to carbonyl carbon in the formamide group with anintensity ratio of 1.00 at 162 ppm.

From the results of NMR spectra, the functional group proportions (molarproportion) ((III)+(IV))/(V) and --NH--CHO group/NH₂ group weredetermined to be 100/0 and 100/0, respectively.

EXAMPLE 4

In the same reaction vessel as used in Example 1 were charged 200 ml ofDMF, 50.5 g of ethylenediamine hydrochloride obtained in ReferenceExample 2 and 200 ml of cumene. The mixture was heated to a temperatureof 80° C. to make a solution. A solution of 70 g of a styrene-maleicanhydride copolymer (NMP-4) (molar proportion: 75/25) (Mw: 12,000; Mn:5,000) in 200 ml of cumene was then gradually added dropwise to thesolution through the dropping funnel.

The reaction solution was then heated to a temperature of about 153° C.where the reaction was allowed to continue for 9 hours, while removingwater produced by azeotropy through the Dean-Stark water separator. Theresulting reaction mixture was charged in 5 l of isopropanol. Theresulting precipitate was dipped in 1,000 ml of a solution of 54 g ofsodium carbonate in a 2:1 (volumetric ratio) mixture of water andisopropanol overnight, filtered off, thoroughly washed with water andisopropanol, and then dried. The yield was 81.0 g.

The copolymer thus obtained (FAP-4) was a white powder which was thendissolved in xylene in a proportion of 10% by weight and measured forviscosity by means of a B type viscometer at a temperature of 25° C. Theresult was 110 cps.

The copolymer thus obtained was then measured for infrared absorptionspectra (KBr tablet method). There were obserbed an absorption the imidering at 1,769 cm⁻¹ and 1,700 cm⁻¹, an absorption by the formamide groupand amide group at 1,662 cm⁻¹ and 1,530 cm⁻¹, and an absorption by theamino group at 3,430 cm⁻¹.

On the other hand, nuclear magnetic resonance spectra (¹³ C-NMR)measured in CDCl₃ showed a peak corresponding to carbonyl carbon in theimide ring with an intensity ratio of 2.00 at 176 to 180 ppm, a peakcorresponding to carbonyl carbon in the formamide group with anintensity ratio of 1.15 at 162 ppm, and a peak corresponding to carbonylcarbon in the amide group with an intensity ratio of 0.26 at 172 to 174ppm.

From the results of NMR spectra, the functional group proportions (molarproportion) ((III)+(IV))/(V) and --NH--CHO group/NH₂ group weredetermined to be 79.4/20.6 and 91/9, respectively.

EXAMPLES 5 TO 10

Copolymers (FAP-5 to FAP-10) were prepared in the same manner as inExample 1 or 3, except that as a diamine salt or a reaction product of adiamine with a formyl group-containing compound there were used thoseobtained in Reference Examples 1 to 9 and as copolymers to be used asstarting materials there were used copolymers (NMP-5 to NMP-10) as setforth in Table 3, respectively. The results are set forth in Table 3.

The copolymers thus obtained were similarly measured for viscosity. Theresults are set forth in Table 3.

                  TABLE 3                                                         ______________________________________                                        Copolymer as starting material                                                                                Amount                                                Kind                    (g)                                           ______________________________________                                        Example 5                                                                             Ethylene-ethyl acrylate-maleic anhydride                                                              100                                           (FAP-5) copolymer (NMP-5) (molar proportion:                                          88/10/2; Mw: 50,000; Mn: 20,000)                                      Example 6                                                                             Styrene-butadiene-maleic anhydride                                                                    100                                           (FAP-6) copolymer (NMP-6) (molar proportion:                                          50/48/2; Mw: 100,000; Mn: 40,000)                                     Example 7                                                                             Ethylene-propylene-maleic anhydride                                                                    83                                           (FAP-7) copolymer (NMP-7) (molar proportion:                                          70/28/2; Mw: 70,000; Mn: 34,000)                                      Example 8                                                                             Ethylene-ethyl acrylate-maleic anhydride                                                               71                                           (FAP-8) copolymer (NMP-8) (molar proportion                                           90/5/5; Mw: 30,000; Mn: 13,000)                                       Example 9                                                                             Ethylene-vinyl acetate-maleic anhydride                                                               100                                           (FAP-6) copolymer (NMP-9) (molar proportion:                                          95/4.5/0.5; Mw: 40,000; Mn: 18,000)                                   Example 10                                                                            Methyl vinyl ether-maleic anhydrid                                                                     47                                           (PAP-10)                                                                              copolymer (NMP-10) (molar proportion:                                         50/50; Mw: 8,000 Mn: 3,900)                                           ______________________________________                                        Diamine salt or reaction product of diamine                                   with formyl group-containing compound                                                                         Amount                                                Kind                    (g)                                           ______________________________________                                        Example 5                                                                             Hexamethylenediamine p-toluene-                                                                       28.5                                                  sulfonate (Reference Example 3)                                       Example 6                                                                             1,3-Bis(aminomethyl)cyclohexanediamine                                                                19.7                                                  p-toluenesulfonate (Reference Example 4)                              Example 7                                                                             m-Xylylenediamine p-toluenesulfonate                                                                  31.8                                                  (Reference Example 5)                                                 Example 8                                                                             Reaction product of 1,3-bis(amino-                                                                    35.0                                                  methyl)cyclohexanediamine with DMF                                            (Reference Example 8)                                                 Example 9                                                                             Reaction product*.sup.1 of m-xylylenediamine                                                           8.6                                                  with formic acid (Reference Example 9)                                Example 10                                                                            Reaction product of ethylenediamine                                                                   36.3                                                  with formamide (Reference Example 6)                                  *.sup.1 1.5 g of triethylamine was used as a catalyst.                        ______________________________________                                        Reaction solvent                                                              Solvent I            Solvent ii                                                       Kind      Amount (ml)                                                                              Kind   Amount (ml)                               ______________________________________                                        Example 5                                                                             DMF       100        Xylene 400                                       Example 6                                                                             DMF        80        Xylene 400                                       Example 7                                                                             DMF       100        Cumene 400                                       Example 8                                                                             --        --         Xylene 500                                       Example 9                                                                             Methyl-    40        Xylene 400                                               formamide                                                             Example 10                                                                            DMF       300        Xylene 300                                       ______________________________________                                        Reaction conditions                                                                   Temperature (°C.)                                                                      Time (hr.)                                                                              Yield (g)                                   ______________________________________                                        Example 5                                                                             140             3         103.1                                       Example 6                                                                             140             6         102.6                                       Example 7                                                                             153             12        85.8                                        Example 8                                                                             140             10        80.7                                        Example 9                                                                             140             5         99.1                                        Example 10                                                                            140             6         69.3                                        ______________________________________                                        Viscosity of copolymer                                                                        Measured  Measured      Color                                                 concent-  temper- Vis-  tone                                         Solvent  ration    ature   cosity                                                                              of co-                                       used     (wt %)    (°C.)                                                                          (cps) polymer                               ______________________________________                                        Example                                                                              Xylene   10        25      450   White                                 Example                                                                              Toluene  10        25      1,480 Pale                                  6                                       yellow                                Example                                                                              Xylene   10        25      980   White                                 7                                                                             Example                                                                              Xylene   10        25      510   White                                 8                                                                             Example                                                                              Xylene   10        25      390   White                                 9                                                                             Example                                                                              DMF      10        25       85   Pale                                  10                                      yellow                                ______________________________________                                                              .sup.13 C-NMR spectra                                          Infrared absorption                                                                          (intensity ratio)                                              spectra (cm.sup.-1)                                                                          W*.sup.1                                                                              Y*.sup.2                                                                             Z*.sup.3                                 ______________________________________                                        Example 5                                                                              3440    amino group  2.00  --   0.36                                          1772    imide ring                                                            1705    imide group                                                           1668    shoulder                                                              1529    formamide group                                              Example 6                                                                              3438    amino group  2.00  --   0.63                                          1775    imide ring                                                            1702    imide ring                                                            1667    shoulder                                                              1530    formamide group                                              Example 7                                                                              3440    amino group  2.00  0.35 1.25                                          1770    imide ring                                                            1700    imide ring                                                            1665    shoulder                                                              1532    formamide group,                                                              amide group                                                  Example 8                                                                              1775    imide ring   2.00  --   1.00                                          1703    imide ring                                                            1668    shoulder                                                              1529    formamide group                                              Example 9                                                                              1780    imide ring   2.00  2.21 3.21                                          1700    imide ring                                                            1660    shoulder                                                              1531    formamide group,                                                              amide group                                                  Example 10                                                                             1779    imide ring   2.00  --   1.00                                          1700    imide ring                                                            1665    shoulder                                                              1528    formamide group,                                                              amide group                                                  *.sup.1 176 to 180 ppm; *.sup.2 172 to 174 ppm; *.sup.3 162                   ______________________________________                                        ppm                                                                                   Functional group proportion                                                     ((III) + (IV))/(V)                                                                          NHCHO/NH.sub.2                                        ______________________________________                                        Example 5 100/0         36/64                                                 Example 6 100/0         63/37                                                 Example 7 74/26         93/7                                                  Example 8 100/0         100/0                                                 Example 9 31/69         100/0                                                 Example 10                                                                              100/0         100/0                                                 ______________________________________                                    

EXAMPLE 11

11.2 g of the copolymer (FAP-4) obtained in Example 4 was dissolved in100 ml of methanol. To the solution was added 50 g of 35% hydrochloricacid. The mixture was then subjected to uniform dispersion. Thedispersion was allowed to stand at room temperature for 2 days. Thereaction mixture was concentrated under reduced pressure and charged in500 ml of isopropanol to obtain a precipitate. The precipitate thusobtained was dipped in 300 ml of a 1:1 (volumetric ratio) mixture ofwater and isopropanol containing 15.0 g of sodium carbonate overnight,filtered off, thoroughly washed with water and isopropanol, and thendried. The yield was 9.3 g.

The copolymer thus obtained (FAP-11) was a white powder which was thendissolved in xylene in a proportion of 10% by weight and measured forviscosity at a temperature of 25° C. The result was 135 cps.

The copolymer thus obtained was then measured for infrared absorptionspectra (KBr tablet method). There were observed an absorption by theimide ring at 1,769 cm^(-l) and 1,700 cm⁻¹, an absorption by the amidegroup at 1,655 cm⁻¹ (shoulder) and 1,530 cm⁻¹, and an absorption by theamino group at 3,430 cm⁻¹.

On the other hand, nuclear magnetic resonance spectra (¹³ C-NMR)measured in CDCl₃ showed a peak corresponding to carbonyl carbon in theimide ring with an intensity ratio of 2.00 at 176 to 180 ppm, no peakcorresponding to carbonyl carbon in the formamide group at 162 ppm, anda peak corresponding to carbonyl carbon in the amide group with anintensity ratio of 0.25 at 172 to 174 ppm.

From the results of NMR spectra, the functional group proportions (molarproportion) ((III)+(IV))/(V) and --NH-CHO group/NH₂ group weredetermined to be 80/20 and 0/100, respectively.

COMPARATIVE EXAMPLE 1

A reaction was attempted to proceed in the same manner as in Example 1,except that 5.0 g of ethylenediamine was used instead of theethylenediamine p-toluenesulfonate and that 300 ml of xylene was usedinstead of DMF. However, after completion of the dropwise addition ofthe styrene-maleic anhydride copolymer solution, when the azeotropy ofwater began during heating, the reaction mixture immediately showed toohigh a viscosity to be stirred and eventually became an integrated mass,disabling the continuance of the reaction.

The mass reaction mixture was partially recovered, washed with methanol,and then dried to obtain a specimen. Even when heated, this specimen wasnot dissolved in xylene. Thus, it was made clear that this productdiffered from the product obtained in Example 1. It was judged that thisproduct comprised a crosslinked structure formed therein.

COMPARATIVE EXAMPLE 2

A reaction was attempted to proceed in the same manner as in Example 3,except that 15 g of hexamethylenediamine was used instead of thereaction product of hexamethylenediamine with DMF. However, when thehexamethylenediamine solution was added dropwise to the system in anamount of about one fourth, the reaction mixture showed too high aviscosity to be stirred, disabling the continuance of the reaction.

The reaction mixture was partially recovered, washed with methanol, andthen dried to obtain a specimen. Even when heated, this specimen was notdissolved in xylene. Thus, it was made clear that this product differedfrom the product obtained in Example 3. It was judged that this productcomprised a crosslinked structure formed therein.

COMPARATIVE EXAMPLE 3

A reaction was attempted to proceed in the same manner as in Example 2,except that 300 ml of DMI was used instead of DMF.

The copolymer (AMP-1) thus obtained was a brown powder which was thendissolved in xylene in a proportion of 10% by weight and measured forviscosity at a temperature of 25° C. The result was 680 cps.

The copolymer thus obtained was then measured for infrared absorptionspectra (KBr tablet method). There were observed an absorption by theimide ring at 1,770 cm⁻¹ and 1,695 cm⁻¹ and an absorption by the aminogroup at 3,425 cm⁻¹.

REFERENCE EXAMPLE 10

(Preparation of maleic anhydride-grafted polypropylene: see JP-B-56-9925(the term "JP-B" as used herein means an "examined Japanese patentpublication"))

100 parts by weight of a crystalline polypropylene powder (NMP-11) witha weight-average molecular weight (Mw) of 60,000 and a number-averagemolecular weight (Mn) of 24,000, 12 parts by weight of maleic anhydrideand 4 parts by weight of dicumyl peroxide were previously mixed. Themixture was then subjected to extrusion reaction in an extruder having ascrew diameter of 30 mm and an L/D ratio of 28 at a barrel temperatureof 230° C. and a screw revolution number of 60 rpm. The grafted compoundwas ground and dipped in acetone to extract away unreacted maleicanhydride. The residue was dried to obtain a maleic anhydride-graftedpolypropylene resin (MMP-1). The amount of the maleic anhydride graftedwas 4.5% by weight. The molecular weight of the product determined bygel permeation chromatography (GPC) was 15,000 (Mw) or 6,500 (Mn) ascalculated in terms of polystyrene.

REFERENCE EXAMPLE 11

Maleic anhydride-grafted copolymers (MMP-2 to MMP-10) set forth in Table4 were prepared in the same manner as in Reference Example 10, exceptthat as copolymers to be used as starting materials there were usedcopolymers (NMP-12 to NMP-20) set forth in Table 4.

                  TABLE 4                                                         ______________________________________                                                                Amount of                                                                     maleic anhydride                                      Copolymers as starting materials                                                                      grafted                                               Kind                    (wt %)                                                ______________________________________                                        MMP-2  Hydrogenated product of styrene-                                                                   1.0                                                      butadiene copolymer (NMP-12)                                                  (weight ratio: 3/7; Mw: 50,000; Mn:                                           48,000)                                                                MMP-3  Ethylene-propylene copolymer                                                                       7.8                                                      (NMP-13) (weight ratio: 1/1;                                                  Mw: 11,800; Mn: 6,600)                                                 MMP-4  Ethylene-propylene copolymer                                                                       0.5                                                      (NMP-14) (weight ratio: 7/3;                                                  Mw: 90,000; Mn: 41,000)                                                MMP-5  Polybutadiene (NMP-15)                                                                             3.7                                                      (Mw: 30,000; Mn: 14,000)                                               MMP-6  Polyethylene (NMP-16)                                                                              20                                                       (Mw: 5,000; Mn: 2,200)                                                 MMP-7  Hydrogenated product of styrene-                                                                   3.1                                                      isoprene copolymer (NMP-17)                                                   (weight ratio: 3/7; Mw: 41,000; Mn:                                           18,200)                                                                MMP-8  Chloroprene rubber (NMP-18)                                                                        2.7                                                      (Mw: 30,000; Mn: 13,000)                                               MMP-9  Nitrile rubber (NMP-19)                                                                            1.8                                                      (Mw: 34,000; Mn: 15,000)                                               MMP-10 Ethylene-ethyl acrylate copolymer                                                                  4.5                                                      (NMP-20) (weight ratio: 17/3;                                                 Mw: 70,000; Mn: 32,000)                                                ______________________________________                                    

EXAMPLE 12

In a 1-l capacity flask equipped with a thermometer, a stirrer, adropping funnel and a Dean-Stark water separator were charged 300 ml ofDMF and 120 g of maleic anhydride-grafted polypropylene (MMP-1) preparedin Reference Example 10. The mixture was heated to a temperature of 140°C. under reflux of xylene to make a solution.

A solution of 17.8 g of ethylenediamine p-toluenesulfonate prepared inReference Example 1 in 200 ml of DMF was gradually added dropwise to thesolution thus obtained in 3 hours. During this process, the reactionmixture was kept at the reflux temperature, and water produced byazeotropy as a result of the imidation reaction was removed from thereaction system through the Dean-Stark water separator.

The reaction was allowed to continue for 14 hours from the beginning ofthe dropwise addition of the above-mentioned ethylenediamine salt. Thereaction mixture was cooled and charged in 5 l of methanol to obtain apurified product which was then recovered as a precipitate.

The precipitate was dissolved in toluene at an elevated temperature. Acast film was then prepared from this solution. The cast film was thenmeasured for infrared absorption spectra. There were observed anabsorption due to the imide ring at 1,768 cm⁻¹ and 1,700 cm⁻¹, anabsorption due to the formamide group at 1,660 cm⁻¹ (shoulder) and 1,530cm⁻¹, and an absorption due to p-toluenesulfonic acid at 1,122 cm⁻¹,1,035 cm⁻¹, 1,010 cm⁻¹, 685 cm⁻¹ and 570 cm⁻¹. It was thus confirmedthat a formamide group or a primary amino group was bonded topolypropylene via an imide bond in the form of p-toluenesulfonic acid.

Further, the precipitate was dipped in a 1:1 (volumetric ratio) mixtureof water and methanol containing 8.0 g of potassium carbonate overnight,filtered off, thoroughly washed with water and methanol, and then dried.The yield was 121.1 g.

The copolymer thus obtained (FAP-12) was a pale yellowish white powderwhich was then dissolved in tetralin at a temperature of 100° C. in aproportion of 10% by weight and measured for viscosity by means of a Btype viscometer at a temperature of 100° C. The result was 180 cps. Axylene cast film was prepared from this solution. The cast film was thenmeasured for infrared absorption spectra. The absorption due top-toluenesulfonic acid at 1,122 cm⁻¹, 1,035 cm⁻¹, 1,010 cm⁻¹, 685 cm⁻¹and 570 cm⁻¹ disappeared. Further, there were observed an absorption bythe imide ring at 1,768 cm⁻¹ and 1,700 cm⁻¹ and an absorption by theformamide group at 1,660 cm⁻¹ (shoulder) and 1,530 cm⁻¹.

Moreover, there was observed an absorption due to the amino group at3,400 cm⁻¹.

On the other hand, nuclear magnetic resonance spectra (¹³ C-NMR)measured with isotope carbon in CDCl₃ showed a peak corresponding tocarbonyl carbon in the imide ring with an intensity ratio of 2.00 at 176to 180 ppm and a peak corresponding to carbonyl carbon in the formamidegroup with an intensity ratio of 0.78 at 162 ppm but no peak indicatingthe presence of carbonyl carbon in the amide group at 172 to 174 ppm.

From the results of NMR spectra, the functional group proportions (molarproportion) ((III-A)+(IV-A))/(V-A) and -NH-CHO group/NH₂ group weredetermined to be 100/0 and 78/22, respectively.

EXAMPLE 13

In the same reaction vessel as used in Example 12 was charged 50 g of aDMF solution containing 10.8 g of hexamethylenediaminep-toluenesulfonate prepared in Reference Example 3. The mixture heatedto a temperature of 80° C.

A solution of 60 g of a maleic anhydride-modified product (MMP-2) (Mw:50,000; Mn: 48,000; amount of maleic anhydride grafted: 1%) as thehydrogenated product of styrene-butadiene copolymer prepared inReference Example 11 in 600 ml of xylene was gradually added dropwise tothe reaction system through the dropping funnel. After completion of thedropwise addition, the reaction mixture was partially recovered for IRspectra. The absorption due to the succinic anhydride ring at 1,780 cm⁻¹completely disappeared.

The reaction was allowed to continue at an elevated temperature of 140°C. for 8 hours while water produced by azeotropy was continuouslyremoved through the Dean-Stark water separator until water was no longerproduced.

After completion of the reaction, the reaction mixture was concentratedto 400 ml under reduced pressure. The concentrate was then charged in 5l of a 1:1 (volumetric ratio) mixture of water and methanol containing6.0 g of sodium carbonate to obtain a product which was then recoveredas a precipitate.

The precipitate was washed with methanol and dried to obtain 59.1 g of adesired copolymer (FAP-13). The copolymer thus obtained was a paleyellowish white powder soluble in xylene. The copolymer was thendissolved in xylene in a proportion of 10% by weight and measured forviscosity by means of a B type viscometer at a temperature of 25° C. Theresult was 790 cps. A xylene cast film was prepared from the copolymer.The cast film was then measured for infrared absorption film. There wereobserved an absorption by the imide ring at 1,775 cm⁻¹ and 1,702 cm⁻¹,an absorption by the formamide group at 1,665 cm⁻¹ (shoulder) and 1,529cm⁻¹, and an absorption (trace) due to the amino group at 3,420 cm⁻¹.

On the other hand, nuclear magnetic resonance spectra (¹³ C-NMR)measured in CDCl₃ showed a peak corresponding to carbonyl carbon in theimide ring with an intensity ratio of 2.00 at 176 to 180 ppm and a peakcorresponding to carbonyl carbon in the formamide group with anintensity ratio of 0.65 ppm at 162 ppm.

From the results of NMR spectra, the functional group proportions (molarproportion) ((III-A)+(IV-A))/(V-A) and -NH-CHO group/NH₂ group weredetermined to be 100/0 and 65/35, respectively.

EXAMPLE 14

In the same reaction vessel as used in Example 12 were charged 90 g of athe maleic anhydride-grafted ethylene-propylene copolymer (MMP-3)prepared in Reference Example 11 and 500 ml of cumene to make asolution.

A solution of 17.7 g of ethylenediamine hydrochloride prepared inReference Example 2 in 80 ml of DMF was added dropwise to the reactionsolution at an elevated temperature of 153° C. under reflux of cumene.

The reaction was allowed to continue for 9 hours while water produced byazeotropy was continuously removed through the Dean-Stark waterseparator until water was no longer produced.

After completion of the reaction, the reaction mixture was then chargedin 5 l of a 1:1 (volumetric ratio) mixture of water and methanolcontaining 10 g of sodium carbonate to obtain a product which was thenrecovered as a precipitate.

The precipitate was washed with methanol and dried to obtain 89.7 g of adesired copolymer (FAP-14). The copolymer thus obtained was a whitepowder soluble in xylene. The copolymer was then dissolved in xylene ina proportion of 10% by weight and measured for viscosity by means of a Btype viscometer at a temperature of 25° C. The result was 350 cps. Axylene cast film was prepared from the copolymer. The cast film was thenmeasured for infrared absorption film. There were observed an absorptionby the imide ring at 1,775 cm⁻¹ and 1,700 cm⁻¹, an absorption by theformamide group at 1,670 cm⁻¹ (shoulder) and 1,529 cm⁻¹, and anabsorption due to the amino group at 3,435 cm⁻¹.

On the other hand, nuclear magnetic resonance spectra (¹³ C-NMR)measured in CDCl₃ showed a peak corresponding to carbonyl carbon in theimide ring with an intensity ratio of 2.00 at 176 to 180 ppm, a peakcorresponding to carbonyl carbon in the formamide group with anintensity ratio of 1.09 ppm at 162 ppm, and a peak corresponding tocarbonyl carbon in the amide group with an intensity of 0.22 at 172 to174 ppm.

From the results of NMR spectra, the functional group proportions (molarproportion) ((III-A)+(IV-A))/(V-A) and -NH-CHO group/NH₂ group weredetermined to be 82/18 and 89/11, respectively.

EXAMPLE 15

A reaction was effected in the same manner as in Example 12, except that120 g of the maleic anhydridegrafted polyethylene (MMP-6) prepared inReference Example 11 was used instead of the maleic anhydride-graftedpolypropylene copolymer and that 45.5 g of the reaction product ofethylenediamine with formamide prepared in Reference Example 6 was usedinstead of ethylenediamine p-toluenesulfonate.

As a result, 134.3 g of a desired copolymer (FAP-15) was obtained. Thecopolymer thus obtained was a white powder soluble in a mixture oftetralin and DMI. The copolymer was then dissolved in a 1:1 (volumetricratio) mixture of tetralin and DMI in a proportion of 10% by weight andmeasured for viscosity by means of a B type viscometer at a temperatureof 100° C. The result was 45 cps. The copolymer was then measured forinfrared absorption spectra (KBr tablet method). There were observed anabsorption by the imide ring at 1,780 cm⁻¹ and 1,772 cm⁻¹ and anabsorption by the formamide group at 1,670 cm⁻¹ (shoulder) and 1,532cm⁻¹.

On the other hand, nuclear magnetic resonance spectra (¹³ C-NMR)measured in CDCl₃ showed a peak corresponding to carbonyl carbon in theimide ring with an intensity ratio of 2.00 at 176 to 180 ppm and a peakcorresponding to carbonyl carbon in the formamide group with anintensity ratio of 0.85 ppm at 162 ppm.

From the results of NMR spectra, the functional group proportions (molarproportion) ((III-A)+(IV-A))/(V-A) and -NH-CHO group/NH₂ group weredetermined to be 100/0 and 85/15, respectively.

EXAMPLES 16 TO 21

Reactions were effected in the same manner as in Examples 12 to 15except that as the diamine salt or reaction product of a diamine with aformyl group-containing compound there were used those obtained inReference Examples 1 to 9 and that as the copolymers to be used asstarting materials there were used copolymers set forth in ReferenceExample 11. The results are set forth in Table 5.

The copolymers thus obtained were similarly measured for viscosity. Theresults are set forth in Table 5.

                  TABLE 5                                                         ______________________________________                                        Copolymers as starting materials                                                      Kind                   Amount (g)                                     ______________________________________                                        Example 16                                                                            Maleic anhydride-grafted ethylene-                                                                   120                                            (FAP-16)                                                                              propylene copolymer (MMP-4)                                           Example 17                                                                            Maleic anhydride-grafted polye                                                                       100                                            (FAP-17)                                                                              butadiene copolymer (MMP-5)                                           Example 18                                                                            Maleic anhydride-grafted styrene-                                                                    100                                            (FAP-18)                                                                              isoprene copolymer (MMP-7)                                            Example 19                                                                            Maleic anhydride-grafted chloroprene                                                                 100                                            (FAP-19)                                                                              rubber (MMP-8)                                                        Example 20                                                                            Maleic anhydride-grafted nitrile                                                                     100                                            (FAP-20)                                                                              rubber (MMP-9)                                                        Example 21                                                                            Maleic anhydride-grafted ethylene-                                                                   100                                            (FAP-21)                                                                              ethyl acrylate copolymer (MMP-10)                                     ______________________________________                                        Diamine salt or reaction product of diamine                                   with formyl group-containing compound                                                 Kind                   Amount (g)                                     ______________________________________                                        Example 16                                                                            Reaction product of hexamethylene-                                                                    4.0                                                   diamine with DMF                                                              (Reference Example 7)                                                 Example 17                                                                            1,3-Bis(aminomethyl)cyclohexane                                                                      19.5                                                   diamine-p-toluenesulfonate                                                    (Reference Example 4)                                                 Example 18                                                                            m-Xylylenediamine p-toluene-                                                                         20.0                                                   sulfonate (Reference Example 5)                                       Example 19                                                                            Reaction product of 1,3-bis(amino-                                                                   10.8                                                   methyl)cyclohexanediamine with DMF                                            (Reference Example 8)                                                 Example 20                                                                            Product*.sup.1 of the reaction of                                                                    10.0                                                   m-xylylenediamine with formic                                                 acid (Reference Example 9)                                            Example 21                                                                            Reaction product of ethylenediamine                                                                  10.6                                                   with formamide (Reference Example 6)                                  *.sup.1 2.0 g of triethylamine was used as a catalyst.                        ______________________________________                                        Reaction solvent                                                              Solvent I            Solvent II                                                       Kind      Amount (ml)                                                                              Kind   Amount (ml)                               ______________________________________                                        Example 16                   Xylene 600                                       Example 17                                                                            DMF       100        Xylene 500                                       Example 18                                                                            DMF       100        Xylene 500                                       Example 19                                                                            Methyl-    50        Xylene 400                                               formamide                                                             Example 20                   Xylene 500                                       Example 21                                                                            DMF       100        Cumene 400                                       ______________________________________                                        Reaction conditions                                                                   Temperature (°C.)                                                                      Time (hr.)                                                                              Yield (g)                                   ______________________________________                                        Example 16                                                                            140             4         117.6                                       Example 17                                                                            140             9         101.5                                       Example 18                                                                            140             3         101.1                                       Example 19                                                                            140             8         101.5                                       Example 20                                                                            140             6         100.3                                       Example 21                                                                            153             14        100.9                                       ______________________________________                                        Viscosity of copolymer                                                                        Measured  Measured      Color                                                 concent-  tempera-                                                                              Vis-  tone                                         Solvent  ration    ture    cosity                                                                              of co-                                       used     (wt %)    (°C.)                                                                          (cps) polymer                               ______________________________________                                        Example                                                                              Xylene   10        25      1,350 White                                 16                                                                            Example                                                                              Xylene   10        25      410   Pale                                  17                                      yellow                                Example                                                                              Xylene   10        25      625   White                                 18                                                                            Example                                                                              Xylene   10        25      390   Pale                                  19                                      yellow                                Example                                                                              Xylene   10        25      450   Pale                                  20                                      yellow                                Example                                                                              Xylene   10        25      510   White                                 21                                                                            ______________________________________                                                              .sup.13 C-NMR spectra                                          Infrared absorption                                                                          (intensity ratio)                                              spectra (cm.sup.-1)                                                                          W*.sup.1                                                                              Y*.sup.2                                                                             Z*.sup.3                                 ______________________________________                                        Example 16                                                                             1772    imide ring   2.00  --   1.00                                          1702    imide ring                                                            1672    shoulder                                                              1529    formamide group                                              Example 17                                                                             3432    amino group  2.00  --   0.81                                          1778    imide ring                                                            1702    imide ring                                                            1667    shoulder                                                              1531    formamide group                                              Example 18                                                                             3450    amino group  2.00  --   0.65                                          1769    imide ring                                                            1695    imide ring                                                            1658    shoulder                                                              1530    formamide group                                              Example 19                                                                             1775    imide ring   2.00  --   1.00                                          1700    imide ring                                                            1665    shoulder                                                              1531    formamide group                                              Example 20                                                                             1770    imide ring   2.00  2.57 3.57                                          1700    imide ring                                                            1668    shoulder                                                              1532    formamide group,                                                              amide group                                                  Example 21                                                                             1772    imide ring   2.00  0.41 1.41                                          1698    imide ring                                                            1662    shoulder                                                     ______________________________________                                        *.sup.1 176 to 180 ppm; *.sup.2 172 to 174 ppm; *.sup.3 162                   ______________________________________                                        ppm                                                                                   Functional group proportion                                                     ((III-A) + (IV-A))/(V-A)                                                                       NHCHO/NH.sub.2                                     ______________________________________                                        Example 16                                                                              100/0            100/0                                              Example 17                                                                              100/0            81/19                                              Example 18                                                                              100/0            35/65                                              Example 19                                                                              100/0            100/0                                              Example 20                                                                              28/72            100/0                                              Example 21                                                                              71/29            100/0                                              ______________________________________                                    

EXAMPLE 22

13.0 g of the copolymer obtained in Example 14 was dissolved in 100 mlof methanol. To the solution was added 50 g of 35% hydrochloric acid.The mixture was then subjected to uniform dispersion. The mixture wasallowed to stand at room temperature for 2 days. The reaction mixturewas concentrated under reduced pressure and charged in 500 ml ofisopropanol to obtain a precipitate. The precipitate thus obtained wasdipped in 300 ml of a 1:1 (volumetric ratio) mixture of water andisopropanol containing 5.0 g of sodium carbonate overnight, filteredoff, thoroughly washed with water and isopropanol, and then dried. Theyield was 12.1 g.

The copolymer thus obtained was a pale yellowish white powder which wasthen dissolved in toluene in a proportion of 10% by weight and measuredfor viscosity at a temperature of 25° C. The result was 395 cps.

A toluene cast film was prepared from the copolymer. The cast film wasthen measured for infrared absorption spectra. There were observed anabsorption by the imide ring at 1,772 cm⁻¹ and 1,700 cm⁻¹, an absorptionby the amide group at 1,666 cm⁻¹ (shoulder) and 1,530 cm⁻¹, and anabsorption by the amino group at 3,430 cm⁻¹.

On the other hand, nuclear magnetic resonance spectra (¹³ C-NMR)measured in CDCl₃ showed a peak corresponding to carbonyl carbon in theimide ring with an intensity ratio of 2.00 at 176 to 180 ppm, no peakcorresponding to carbonyl carbon in the formamide group at 162 ppm, anda peak corresponding to carbonyl carbon in the amide group with anintensity ratio of 0.20 at 172 to 174 ppm.

From the results of NMR spectra, the functional group proportions (molarproportion) (IV-A)/(V-A) and -NH-CHO group/NH₂ group were determined tobe 83/17 and 0/100, respectively.

COMPARATIVE EXAMPLE 4

A reaction was attempted to proceed in the same manner as in Example 12,except that 5.0 g of the ethylenediamine was used instead of theethylenediamine p-toluenesulfonate and that 200 ml of xylene was usedinstead of DMF. However, when the amount of a solution of 17.8 g ofethylenediamine p-toluenesulfonate in 200 ml of DMF added dropwisereached one fifth of the amount of the ethylenediamine solution, thereaction mixture immediately showed too high a viscosity to be stirredand eventually became an integrated mass, disabling the continuance ofthe reaction.

The mass reaction mixture was partially recovered, washed with methanol,and then dried to obtain a specimen. Even when heated, this specimen wasnot dissolved in xylene. Thus, it was made clear that this productdiffered from the product obtained in Example 12. It was judged thatthis product comprised a crosslinked structure formed therein.

COMPARATIVE EXAMPLE 5

In the same reaction vessel as used in Example 2 were charged 800 ml ofxylene and 16.5 g of ethylenediamine. The mixtre was heated to atemperature of 100° C. 120 g of the maleic anhydride-graftedpolypropylene obtained in Reference Example 10 was added to the reactionsystem in the form of a powder. The reaction system continued to beheated. However, when the azeotropy of water began, the reaction mixtureimmediately showed too high a viscosity to be stirred and eventuallybecame an integrated mass, disabling the continuance of the reaction.

The mass reaction mixture was partially recovered, washed with methanol,and then dried to obtain a specimen. Even when heated, this specimen wasnot dissolved in xylene. Thus, it was made clear that this productdiffered from the product obtained in Example 12. It was judged thatthis-product comprised a crosslinked structure formed therein.

COMPARATIVE EXAMPLE 6

A reaction was attempted to proceed in the same manner as in Example 13,except that 4.5 g of hexaethylenediamine was used instead of theethylenediamine p-toluenesulfonate and that 150 ml of xylene was usedinstead of DMF. However, after completion of the dropwise addition of asolution of 60 g of a maleic anhydride-modified product (MMP-2) (Mw:50,000; Mn: 48,000; amount of maleic anhydride grafted: 1%) as thehydrogenated product of styrenebutadiene copolymer in 600 ml of xylene,when the distillation of water by azeotropy began during heating, thereaction mixture immediately showed too high a viscosity to be stirredand eventually became an integrated mass, disabling the continuance ofthe reaction.

The mass reaction mixture was partially recovered, washed with methanol,and then dried to obtain a specimen. Even when heated, this specimen wasnot dissolved in xylene. Thus, it was made clear that this productdiffered from the product obtained in Example 13. It was judged thatthis product comprised a crosslinked structure formed therein.

COMPARATIVE EXAMPLE 7

A reaction was attempted to proceed in the same manner as in Example 12,except that 200 ml of DMI was used instead of DMF. The copolymer thusobtained was a brown powder soluble in xylene. The copolymer was thendissolved in tetralin in a proportion of 10% by weight for themeasurement of viscosity at a temperature of 100° C. The result was 165cps.

A xylene cast film was prepared from the copolymer for the measurementof IR spectra. There were observed an absorption by the imide ring at1,770 cm⁻¹ and 1,700 cm⁻¹ and an absorption by the amino group at 3,350cm⁻¹.

EXAMPLES 23 TO 75 & COMPARATIVE EXAMPLES 8 TO 61

Predetermined components (i) and (ii) set forth in Tables 6 and 7 andcomponents (iii) consisting of the above-mentioned amino-modifiedproduct or acid copolymer were dry-blended, thoroughly dried, and thenthoroughly kneaded by means of an NVC single screw-extruder (produced byNakatani Kikai K.K.) with a vent. The mixture was then molded by a TypeIS100EN injection molding machine (produced by Toshiba Machine Co.,Ltd.) to prepare test pieces.

Using the test pieces thus obtained, various physical properties wereevaluated in accordance with the following methods. The results are setforth in Table 8.

(1) Izod impact test: effected in accordance with JIS-K-7110(Conditions) temperature: 23° C.,-30° C.; notched; n=5

(2) Face impact test: An automatic falling weight impact test waseffected to determine fracture condition and fracture energy.

(Method) A 80×80×3 mm injection-molded plate was fixed to a specimenclamping plate having a hole with a diameter of 2 inch in such anarrangement that the center of the injection-molded plate met the centerof the hole of the specimen clamping plate. Under the conditionsdescribed below, a displacement curve with respect to the force wasdetermined. From the displacement curve, the area up to the displacementpoint at which the force showed a rapid drop was determined as afracture energy [J]. After completion of the test, the fracturecondition was observed to evaluate if the specimen was ductile (D),slightly ductile, slightly brittle (B') or brittle (B).

(Condition) temperature: -10° C.; load of weight: 3.75 kg; speed ofweight: 7.0 m/sec.; n=5; The tester used was RDT5000 (produced byRheometrix Corp.).

(3) Peelability: effected in accordance with cross-cut peel test method

(Method) A 80×80×3 mm injection-molded plate (prepared with a constantinjection time and filling time) was notched with a sharp cutter bladein a 10×10 mm square on the center portion thereof so as to give 100squares having a size of 1×1 mm. A cellophane adhesive tape was thenstrongly put onto these squares. The cellophane adhesive tape wassuddenly peeled off the plate at an angle of 45°. The percent remainingwas defined below. This test was effected 5 times for each specimen. Themeasurements were then averaged for evaluation of peelability.

(Percent remaining)=(remaining number of 1×1 mm squares)/100

(4) External appearance: Poor appearances such as flow mark, stripepattern, fluffing and silver blister were visually evaluated. Criterion:E (Good); F (slightly poor); P (poor)

                  TABLE 6                                                         ______________________________________                                        (resin as component (i))                                                      Abbreviation                                                                              Name of resin     Grade                                           ______________________________________                                        PC-1        Polycarbonate     A2200*.sup.2                                    PC-2        Polycarbonate     A2500*.sup.3                                    PC-3        Polyarylate       U100T*.sup.4                                    PET-1       Polyethylene terephthalate                                                                      PA200*.sup.5                                    PBT-1       Polybutylene terephthalate                                                                      N1000.sup.*6                                    PA-1        Polyamide-6       1013*.sup.7                                     PA-2*.sup.1 Polyamide-6       1012C*.sup.8                                    PA-3        Polyamide-6,6     CM3007*.sup.9                                   POM-1       Polyoxymethylene  M25*.sup.10                                     PPE-1       Polyphenylene ether                                                                             SE100J*.sup.11                                  ______________________________________                                         *.sup.1 Abundantly terminated with carboxylic acid; the ratio of              carboxylic acid to amino group at end is 9:1                                  *.sup.2 Tuflon, produced by Idemitsu Petrochemical Co., Ltd.                  *.sup.3 Tuflon, produced by Idemitsu Petrochemical Co., Ltd.                  *.sup.4 U Polymer, produced by Unitika Ltd.                                   *.sup.5 Dianite, produced by Mitsubishi Rayon Co., Ltd.                       *.sup.6 Tufpet, produced by Mitsubishi Rayon Co., Ltd.                        *.sup.7 Ube Nylon, produced by Ube Industries, Ltd.                           *.sup.8 Ube Nylon, produced by Ube Industris, Ltd.                            *.sup.9 Alamine, produced by Toray Industries, Inc.                           *.sup.10 Duracon, produced by Polyplastics Co., Ltd.                          *.sup.11 Noryl, produced by Nippon GE Plastics K.K.                      

                  TABLE 7                                                         ______________________________________                                        (resin as component (ii))                                                     Abbreviation                                                                           Name of resin         Grade                                          ______________________________________                                        PP-1     Polypropylene         J-465H*.sup.12                                 PP-2     Polypropylene         J-609H*.sup.13                                 PP-3     Polypropylene         E100G*.sup.14                                  PE-1     Polyethylene          750LB*.sup.15                                  EP-1     Ethylene-propylene rubber                                                                           EP912P*.sup.16                                 PS-1     General-purpose polystyrene                                                                         US300*.sup.17                                  PS-2     High impact polystyrene                                                                             HT52*.sup.18                                   ABS-1    ABS resin             DP611*.sup.19                                  AS-1     AS resin              290SF*.sup.20                                  SMA-1    Styrene-maleic anhydride copolymer                                                                  UG830*.sup.21                                  ______________________________________                                         *.sup.12 Idemitsu Polypro, block polypropylene produced by Idemitsu           Petrochemical Co., Ltd.                                                       *.sup.13 Ube Polypro, block polypropylene produced by Ube Industries, Ltd     *.sup.14 Idemitsu Polypro, homopolypropylene produced by Idemitsu             Petrochemical Co., Ltd.                                                       *.sup.15 Idemitsu Polyethylene, produced by Idemitsu Petrochemical Co.,       Ltd.                                                                          *.sup.16 JSR EP, produced by JSR                                              *.sup.17 Idemitsu Styrol, GPPS produced by Idemitsu Petrochemical Co.,        Ltd.                                                                          *.sup.18 Idemitsu Styrol, HIPS produced by Idemitsu Petrochemical Co.,        Ltd.                                                                          *.sup.19 JSR ABS, produced by JSR                                             *.sup.20 JSR AS, produced by JSR                                              *.sup.21 Moremax, produced by Idemitsu Petrochemical Co., Ltd.           

                  TABLE 8                                                         ______________________________________                                               Resin formulations                                                              Component (i)                                                                             Component (ii)                                                                            Component (iii)                                       (wt. %)*.sup.a                                                                            (wt. %)*.sup.a                                                                            (wt. %)*.sup.b                               ______________________________________                                        Example 23                                                                             PC-1 (90)   PP-1 (10)   FAP-2 (2)                                    Example 24                                                                             PC-1 (70)   PP-1 (30)   FAP-5 (5)                                    Example 25                                                                             PC-1 (30)   PP-1 (70)   FAP-6 (5)                                    Example 26                                                                             PC-1 (10)   PP-2 (90)   FAP-9 (10)                                   Example 27                                                                             PC-2 (5)    PP-3 (95)   FAP-1 (5)                                    Comparative                                                                            PC-1 (90)   PP-1 (10)    -- (--)                                     Example 8                                                                     Comparative                                                                            PC-1 (70)   PP-1 (30)   NMP-5 (5)                                    Example 9                                                                     Comparative                                                                            PC-1 (30)   PP-1 (70)   NMP-6 (5)                                    Example 10                                                                    Comparative                                                                            PC-1 (10)   PP-2 (90)   NMP-8 (10)                                   Example 11                                                                    Comparative                                                                            PC-2 (5)    PP-3 (95)   NMP-1 (5)                                    Example 12                                                                    Example 28                                                                             PC-1 (70)   PE-1 (30)   FAP-7 (5)                                    Example 29                                                                             PC-3 (30)   PE-1 (70)   FAP-10 (2)                                   Example 30                                                                             PC-1 (95)   EP-1 (5)    FAP-7 (5)                                    Comparative                                                                            PC-1 (70)   PE-1 (30)   NMP-7 (5)                                    Example 13                                                                    Comparative                                                                            PC-3 (30)   PE-1 (70)   NMP-10 (2)                                   Example 14                                                                    Comparative                                                                            PC-3 (30)   PE-1 (70)   FAP-10 (25)                                  Example 15                                                                    Comparative                                                                            PC-1 (95)   EP-1 (5)    EP-1 (5)                                     Example 16                                                                    Example 31                                                                             PC-1 (70)   PS-1 (30)   FAP-6 (2)                                    Example 32                                                                             PC-1 (30)   ABS-1 (70)  FAP-1 (5)                                    Example 33                                                                             PC-3 (50)   ABS-1 (50)  FAP-3 (5)                                    Example 34                                                                             PC-2 (70)   SMA-1 (30)  FAP-4 (5)                                    Comparative                                                                            PC-1 (70)   PS-1 (30)    --                                          Example 17                                                                    Comparative                                                                            PC-1 (30)   ABS-1 (70)  AMP-1 (5)                                    Example 18                                                                    Comparative                                                                            PC-3 (50)   ABS-1 (50)  NMP-3 (5)                                    Example 19                                                                    Comparative                                                                            PC-2 (70)   SMA-1 (30)  SMA-1 (5)                                    Example 20                                                                    Example 35                                                                             PBT-1 (70)  PE-1 (30)   FAP-9 (5)                                    Example 36                                                                             PET-1 (95)  EP-1 (5)    FAP-7 (2)                                    Example 37                                                                             PBT-1 (50)  ABS-1 (50)  FAP-4 (10)                                   Example 38                                                                             PET-1 (70)  ABS-1 (30)  FAP-3 (5)                                    Example 39                                                                             PBT-1 (70)  PS-2 (30)   FAP-6 (5)                                    Comparative                                                                            PBT-1 (70)  PE-1 (30)   NMP-9 (5)                                    Example 21                                                                    Comparative                                                                            PET-1 (95)  EP-1 (5)     --                                          Example 22                                                                    Comparative                                                                            PBT-1 (50)  ABS-1 (50)  NMP-4 (10)                                   Example 23                                                                    Comparative                                                                            PET-1 (70)  ABS-1 (30)   --                                          Example 24                                                                    Comparative                                                                            PBT-1 (70)  PS-2 (30)   NMP-6 (5)                                    Example 25                                                                    Example 40                                                                             PA-1 (90)   EP-1 (10)   FAP-7 (5)                                    Example 41                                                                             PA-1 (70)   ABS-1 (30)  FAP-6 (5)                                    Example 42                                                                             PA-2 (70)   ABS-1 (30)  FAP-6 (5)                                    Example 43                                                                             PA-3 (70)   SMA-1 (30)  FAP-1 (2)                                    Comparative                                                                            PA-1 (90)   EP-1 (10)   EP-1 (5)                                     Example 26                                                                    Comparative                                                                            PA-1 (70)   ABS-1 (30)   --                                          Example 27                                                                    Comparative                                                                            PA-3 (70)   SMA-1 (30)  AMP-1 (10)                                   Example 28                                                                    Example 44                                                                             POM-1 (95)  EP-1 (5)    FAP-7 (2)                                    Example 45                                                                             PPE-1 (70)  PP-1 (30)   FAP-8 (5)                                    Example 46                                                                             PPE-1 (50)  ABS-1 (50)  FAP-4 (7)                                    Comparative                                                                            POM-1 (95)  EP-1 (5)     --                                          Example 29                                                                    Comparative                                                                            PPE-1 (70)  PP-1 (30)   NMP-8 (5)                                    Example 30                                                                    Comparative                                                                            PPE-1 (50)  ABS-1 (50)  NMP-4 (7)                                    Example 31                                                                    Example 47                                                                             PC-1 (90)   PP-1 (10)   FAP-13 (2)                                   Example 48                                                                             PC-1 (70)   PP-1 (30)   FAP-12 (5)                                   Example 49                                                                             PC-1 (30)   PP-1 (70)   FAP-13 (5)                                   Example 50                                                                             PC-1 (10)   PP-1 (90)   FAP-21 (10)                                  Example 51                                                                             PC-2 (5)    PP-2 (95)   FAP-18 (5)                                   Comparative                                                                            PC-1 (90)   PP-1 (10)   NMP-12 (2)                                   Example 32                                                                    Comparative                                                                            PC-1 (70)   PP-1 (30)    --                                          Example 33                                                                    Comparative                                                                            PC-1 (70)   PP-1 (30)   AMP-1 (5)                                    Example 34                                                                    Comparative                                                                            PC-1 (30)   PP-1 (70)   BP-1 (5)                                     Example 35                                                                    Comparative                                                                            PC-1 (10)   PP-1 (90)   NMP-20 (10)                                  Example 36                                                                    Example 52                                                                             PC-1 (70)   PE-1 (30)   FAP-15 (5)                                   Example 53                                                                             PC-1 (30)   PE-1 (70)   FAP-17 (2)                                   Example 54                                                                             PC-1 (95)   EP-1 (5)    FAP-16 (5)                                   Comparative                                                                            PC-2 (5)    PP-2 (95)   NMP-17 (5)                                   Example 37                                                                    Comparative                                                                            PC-1 (70)   PE-1 (30)    --                                          Example 38                                                                    Comparative                                                                            PC-1 (30)   PE-1 (70)   NMP-16 (2)                                   Example 39                                                                    Comparative                                                                            PC-1 (95)   EP-1 (5)    NMP-15 (5)                                   Example 40                                                                    Example 55                                                                             PC-3 (70)   ABS-1 (30)  FAP-18 (5)                                   Example 56                                                                             PC-1 (70)   ABS-1 (30)  FAP-13 (5)                                   Example 57                                                                             PC-1 (90)   PS-1 (10)   FAP-13 (5)                                   Example 58                                                                             PC-1 (30)   AS-1 (70)   FAP-20 (10)                                  Comparative                                                                            PC-3 (70)   ABS-1 (30)  MMP-7 (5)                                    Example 41                                                                    Comparative                                                                            PC-1 (70)   ABS-1 (30)   --                                          Example 42                                                                    Comparative                                                                            PC-1 (90)   PS-1 (10)    --                                          Example 43                                                                    Comparative                                                                            PC-1 (30)   AS-1 (70)   MMP-9 (10)                                   Example 44                                                                    Example 59                                                                             PC-2 (70)   SMA-1 (30)  FAP-13 (2)                                   Example 60                                                                             PET-1 (50)  PE-1 (50)   FAP-18 (5)                                   Example 61                                                                             PBT-1 (30)  PP-1 (70)   FAP-12 (2)                                   Example 62                                                                             PET-1 (90)  EP-1 (10)   FAP-16 (2)                                   Example 63                                                                             PET-1 (30)  SMA-1 (70)  FAP-21 (5)                                   Comparative                                                                            PC-2 (70)   SMA-1 (30)  MMP-2 (2)                                    Example 45                                                                    Comparative                                                                            PET-1 (50)  PE-1 (50)   MMP-7 (5)                                    Example 46                                                                    Comparative                                                                            PBT-1 (30)  PP-3 (70)   AMP-1 (2)                                    Example 47                                                                    Comparative                                                                            PET-1 (90)  EP-1 (10)    --                                          Example 48                                                                    Comparative                                                                            PET-1 (30)  SMA-1 (70)  MMP-20 (5)                                   Example 49                                                                    Example 64                                                                             PBT-1 (50)  ABS-1 (50)  FAP-13 (5)                                   Example 65                                                                             PA-1 (30)   PP-1 (70)   FAP-12 (5)                                   Example 66                                                                             PA-1 (70)   PE-1 (30)   FAP-15 (5)                                   Example 67                                                                             PA-1 (70)   PE-1 (30)   FAP-15 (5)                                   Comparative                                                                            PBT-1 (50)  ABS-1 (50)  NMP-2 (5)                                    Example 50                                                                    Comparative                                                                            PA-1 (30)   PP-2 (70)   FAP-12 (25)                                  Example 51                                                                    Comparative                                                                            PA-1 (30)   PP-2 (70)   PP-2 (25)                                    Example 52                                                                    Example 68                                                                             PA-3 (90)   EP-1 (10)   FAP-16 (2)                                   Example 69                                                                             PA-3 (30)   ABS-1 (70)  FAP-18 (2)                                   Example 70                                                                             PA-1 (90)   PS-2 (10)   FAP-18 (10)                                  Comparative                                                                            PA-1 (70)   EP-1 (30)    --                                          Example 53                                                                    Comparative                                                                            PA-3 (90)   EP-1 (10)    --                                          Example 54                                                                    Comparative                                                                            PA-1 (30)   ABS-1 (70)  NMP-14 (2)                                   Example 55                                                                    Example 71                                                                             PA-1 (70)   SMA-1 (30)  FAP-13 (5)                                   Example 72                                                                             POM-1 (95)  EP-1 (5)    FAP-14 (5)                                   Example 73                                                                             PPE-1 (30)  PE-1 (70)   FAP-14 (5)                                   Example 74                                                                             PPE-1 (70)  ABS-1 (30)  FAP-13 (5)                                   Example 75                                                                             PPE-1 (70)  SMA-1 (30)  FAP-18 (5)                                   Comparative                                                                            PA-3 (90)   PS-2 (10)   MMP-7 (10)                                   Example 56                                                                    Comparative                                                                            PA-1 (70)   SMA-1 (30)  NMP-12 (5)                                   Example 57                                                                    Comparative                                                                            POM-1 (95)  EP-1 (5)    MMP-3 (5)                                    Example 58                                                                    Comparative                                                                            PPE-1 (30)  PE-1 (70)    --                                          Example 59                                                                    Comparative                                                                            PPE-1 (70)  ABS-1 (30)  MMP-2 (5)                                    Example 60                                                                    Comparative                                                                            PPE-13 (70) SMA-1 (30)  NMP-17 (5)                                   Example 61                                                                    ______________________________________                                                 Physical properties                                                           Impact strength*.sup.c                                                                           Color                                                        23° C.                                                                           -30° C.                                                                           tone                                          ______________________________________                                        Example 23 70.3      43.4       White                                         Example 24 63.2      40.4       White                                         Example 25 42.7      30.0       White                                         Example 26 37.4      19.7       White                                         Example 27 26.3      12.4       White                                         Comparative                                                                              53.2      8.8        White                                         Example 8                                                                     Comparative                                                                              22.4      10.3       White                                         Example 9                                                                     Comparative                                                                              13.2      7.1        White                                         Example 10                                                                    Comparative                                                                              14.1      8.9        White                                         Example 11                                                                    Comparative                                                                              7.2       2.1        White                                         Example 12                                                                    Example 28 58.1      22.8       White                                         Example 29 17.3      7.9        Pale brown                                    Example 30 75.4      42.1       White                                         Comparative                                                                              18.7      12.0       White                                         Example 13                                                                    Comparative                                                                              6.4       1.1        Pale brown                                    Example 14                                                                    Comparative                                                                              10.4      4.1        Pale brown                                    Example 15                                                                    Comparative                                                                              76.9      27.3       White                                         Example 16                                                                    Example 31 30.2      20.9       White                                         Example 32 N.B.      48.6       Pale yellow                                   Example 33 44.9      27.1       Pale yellow                                   Example 34*.sup.e                                                                        80 or more                                                                              48.2       White                                         Comparative                                                                              8.2       2.3        White                                         Example 17                                                                    Comparative                                                                              15.2      8.0        Brown                                         Example 18                                                                    Comparative                                                                              30.3      9.9        Pale yellow                                   Example 19                                                                    Comparative                                                                              80 or more                                                                              20.3       White                                         Example 20*.sup.h                                                             Example 35 40.7      26.3       White                                         Example 36 37.6      28.5       White                                         Example 37 52.3      27.8       Pale yellow                                   Example 38 30.8      20.1       Pale yellow                                   Example 39 25.2      14.0       White                                         Comparative                                                                              7.6       3.2        White                                         Example 21                                                                    Comparative                                                                              13.2      6.3        White                                         Example 22                                                                    Comparative                                                                              7.9       2.2        Pale brown                                    Example 23                                                                    Comparative                                                                              6.3       2.2        Pale brown                                    Example 24                                                                    Comparative                                                                              8.3       3.5        White                                         Example 25                                                                    Example 40 54.3      27.6       White                                         Example 41 57.4      40.8       Pale yellow                                   Example 42 62.7      44.3       Pale yellow                                   Example 43 37.8      19.6       White                                         Comparative                                                                              29.3      10.4       White                                         Example 26                                                                    Comparative                                                                              19.9      8.7        Pale yellow                                   Example 27                                                                    Comparative                                                                              38.4      18.3       Brown                                         Example 28                                                                    Example 44 24.8      15.2       White                                         Example 45 32.3      16.2       Pale yellow                                   Example 46 43.7      23.4       Pale yellow                                   Comparative                                                                              8.6       3.2        White                                         Example 29                                                                    Comparative                                                                              10.4      4.2        Pale yellow                                   Example 30                                                                    Comparative                                                                              20.0      12.3       Pale yellow                                   Example 31                                                                    Example 47 76.5      42.5       White                                         Example 48 62.8      40.1       White                                         Example 49 42.3      27.6       White                                         Example 50 41.9      23.3       White                                         Example 51 15.9      9.8        Pale yellow                                   Comparative                                                                              34.0      5.3        White                                         Example 32                                                                    Comparative                                                                              5.3       3.1        White                                         Example 33                                                                    Comparative                                                                              60.4      40.2       Pale brown                                    Example 34                                                                    Comparative                                                                              36.5      12.3       White                                         Example 35                                                                    Comparative                                                                              22.4      7.3        White                                         Example 36                                                                    Example 52 50.5      24.8       White                                         Example 53 32.3      20.4       White                                         Example 54 72.6      40.3       White                                         Comparative                                                                              72.6      40.3       Pale yellow                                   Example 37                                                                    Comparative                                                                              4.7       1.5        White                                         Example 38                                                                    Comparative                                                                              12.7      7.6        White                                         Example 39                                                                    Comparative                                                                              50.2      14.5       White                                         Example 40                                                                    Example 55 36.8      19.7       Pale yellow                                   Example 56 69.6      40.0       Pale yellow                                   Example 57 34.3      20.8       White                                         Example 58 23.8      12.4       Pale yellow                                   Comparative                                                                              20.6      8.9        Pale yellow                                   Example 41                                                                    Comparative                                                                              62.4      37.3       Pale yellow                                   Example 42                                                                    Comparative                                                                              24.2      14.3       White                                         Example 43                                                                    Comparative                                                                              13.1      3.2        Pale yellow                                   Example 44                                                                    Example 59 37.9      24.3       White                                         Example 60 39.7      25.4       White                                         Example 61 33.7      14.8       White                                         Example 62 40.3      23.0       White                                         Example 63 23.6      13.5       White                                         Comparative                                                                              15.4      5.3        White                                         Example 45                                                                    Comparative                                                                              13.2      6.3        White                                         Example 46                                                                    Comparative                                                                              36.7      15.0       Pale brown                                    Example 47                                                                    Comparative                                                                              20.9      7.4        White                                         Example 48                                                                    Comparative                                                                              10.3      2.3        White                                         Example 49                                                                    Example 64 60.4      23.6       Pale yellow                                   Example 65 32.7      19.9       White                                         Example 66 64.2      30.9       White                                         Example 67 70.8      34.6       White                                         Comparative                                                                              52.4      13.1       Pale yellow                                   Example 50                                                                    Comparative                                                                              23.5      10.4       White                                         Example 51                                                                    Comparative                                                                              8.9       2.1        White                                         Example 52                                                                    Example 68 54.9      31.2       White                                         Example 69 62.5      43.1       Pale yellow                                   Example 70 35.6      17.7       White                                         Comparative                                                                              5.8       2.6        White                                         Example 53                                                                    Comparative                                                                              26.4      7.3        White                                         Example 54                                                                    Comparative                                                                              30.4      17.5       Pale yellow                                   Example 55                                                                    Example 71 33.8      20.0       White                                         Example 72 25.6      14.2       White                                         Example 73 23.8      14.5       Pale yellow                                   Example 74 40.5      26.3       Pale yellow                                   Example 75 23.9      13.6       Pale yellow                                   Comparative                                                                              23.2      12.3       White                                         Example 56                                                                    Comparative                                                                              20.1      8.8        White                                         Example 57                                                                    Comparative                                                                              13.6      6.3        White                                         Example 58                                                                    Comparative                                                                              8.9       2.0        Pale yellow                                   Example 59                                                                    Comparative                                                                              26.3      10.1       Pale yellow                                   Example 60                                                                    Comparative                                                                              17.3      8.0        Pale yellow                                   Example 61                                                                    ______________________________________                                                Physical properties                                                           Face impact strength   External                                                 Fracture Fracture   Peel-  appear-                                            condition                                                                              energy (J) ability*.sup.1                                                                       ance*.sup.j                              ______________________________________                                        Example 23                                                                              D        34         100/100                                                                              E                                        Example 24                                                                              D        27         100/100                                                                              E                                        Example 25                                                                              D        23         100/100                                                                              E                                        Example 26                                                                              D'       15         100/100                                                                              E                                        Example 27*.sup.e                                                                       B'        9         100/100                                                                              E                                        Comparative                                                                             B         5          70/100                                                                              F                                        Example 8                                                                     Comparative                                                                             B         1          37/100                                                                              P                                        Example 9                                                                     Comparative                                                                             B         2          17/100                                                                              P                                        Example 10                                                                    Comparative                                                                             B         3          33/100                                                                              P                                        Example 11                                                                    Comparative                                                                             B         1         100/100                                                                              P                                        Example 12                                                                    Example 28                                                                              D        23         100/100                                                                              E                                        Example 29                                                                              B'        8          77/100                                                                              E                                        Example 30                                                                              D        35         100/100                                                                              E                                        Comparative                                                                             B'        4          20/100                                                                              P                                        Example 13                                                                    Comparative                                                                             B         1          0/100 P                                        Example 14                                                                    Comparative                                                                             B         4         100/100                                                                              F                                        Example 15                                                                    Comparative                                                                             D'       13         100/100                                                                              E                                        Example 16                                                                    Example 31                                                                              D'       22         100/100                                                                              E                                        Example 32                                                                              D        26         100/100                                                                              E                                        Example 33                                                                              D'       20         100/100                                                                              E                                        Example 34                                                                              D        50         100/100                                                                              E                                        Comparative                                                                             B         1          35/100                                                                              F                                        Example 17                                                                    Comparative                                                                             B         3          65/100                                                                              E                                        Example 18                                                                    Comparative                                                                             B         4          40/100                                                                              E                                        Example 19                                                                    Comparative                                                                             D        34         100/100                                                                              E                                        Example 20                                                                    Example 35                                                                              D        20         100/100                                                                              E                                        Example 36                                                                              D'       18         100/100                                                                              E                                        Example 37                                                                              D        22         100/100                                                                              E                                        Example 38                                                                              D'       15         100/100                                                                              E                                        Example 39                                                                              D'       12         100/100                                                                              E                                        Comparative                                                                             B         2          19/100                                                                              E                                        Example 21                                                                    Comparative                                                                             B         3         100/100                                                                              E                                        Example 22                                                                    Comparative                                                                             B         3          52/100                                                                              E                                        Example 23                                                                    Comparative                                                                             B         4          79/100                                                                              E                                        Example 24                                                                    Comparative                                                                             B         3          95/100                                                                              E                                        Example 25                                                                    Example 40                                                                              D        25         100/100                                                                              E                                        Example 41                                                                              D        27         100/100                                                                              E                                        Example 42                                                                              D        30         100/100                                                                              E                                        Example 43                                                                              D'       14         100/100                                                                              E                                        Comparative                                                                             B'        8         100/100                                                                              E                                        Example 26                                                                    Comparative                                                                             B'        5          65/100                                                                              E                                        Example 27                                                                    Comparative                                                                             D'       12         100/100                                                                              E                                        Example 28                                                                    Example 44                                                                              B'       10         100/100                                                                              E                                        Example 45                                                                              D'       14         100/100                                                                              E                                        Example 46                                                                              D'       24         100/100                                                                              E                                        Comparative                                                                             B         1         100/100                                                                              E                                        Example 29                                                                    Comparative                                                                             B         3          23/100                                                                              E                                        Example 30                                                                    Comparative                                                                             B'        8          38/100                                                                              E                                        Example 31                                                                    Example 47                                                                              D        33         100/100                                                                              E                                        Example 48                                                                              D        28         100/100                                                                              E                                        Example 49                                                                              D'       22         100/100                                                                              E                                        Example 50                                                                              D'       20          80/100                                                                              E                                        Example 51                                                                              B'        8          74/100                                                                              E                                        Comparative                                                                             B         4          63/100                                                                              F                                        Example 32                                                                    Comparative                                                                             B         1          10/100                                                                              P                                        Example 33                                                                    Comparative                                                                             D        30         100/100                                                                              E                                        Example 34                                                                    Comparative                                                                             B'        5          6/100 P                                        Example 35                                                                    Comparative                                                                             B         2          2/100 P                                        Example 36                                                                    Example 52                                                                              D        25         100/100                                                                              E                                        Example 53                                                                              D        22         100/100                                                                              E                                        Example 54                                                                              D        34         100/100                                                                              E                                        Comparative                                                                             B         3          4/100 E                                        Example 37                                                                    Comparative                                                                             B         1          7/100 P                                        Example 38                                                                    Comparative                                                                             B'        4          12/100                                                                              P                                        Example 39                                                                    Comparative                                                                             D'       13         100/100                                                                              E                                        Example 40                                                                    Example 55*.sup.f                                                                       D'       20         100/100                                                                              E                                        Example 56                                                                              D        25         100/100                                                                              E                                        Example 57                                                                              D'       23         100/100                                                                              E                                        Example 58                                                                              B'       10         100/100                                                                              E                                        Comparative                                                                             B         3          76/100                                                                              F                                        Example 41                                                                    Comparative                                                                             D'       19          75/100                                                                              E                                        Example 42                                                                    Comparative                                                                             B'        4         100/100                                                                              F                                        Example 43                                                                    Comparative                                                                             B         3         100/100                                                                              F                                        Example 44                                                                    Example 59                                                                              D        25         100/100                                                                              E                                        Example 60                                                                              D'       20         100/100                                                                              E                                        Example 61                                                                              D'       15         100/100                                                                              E                                        Example 62                                                                              D        23         100/100                                                                              E                                        Example 63                                                                              B'        6         100/100                                                                              E                                        Comparative                                                                             B         2         100/100                                                                              F                                        Example 45                                                                    Comparative                                                                             B'        4          35/100                                                                              F                                        Example 46                                                                    Comparative                                                                             D'       16         100/100                                                                              E                                        Example 47                                                                    Comparative                                                                             B'        7         100/100                                                                              F                                        Example 48                                                                    Comparative                                                                             B         2          19/100                                                                              P                                        Example 49                                                                    Example 64                                                                              D        26         100/100                                                                              E                                        Example 65                                                                              D'       19         100/100                                                                              E                                        Example 66                                                                              D        28         100/100                                                                              E                                        Example 67                                                                              D        27         100/100                                                                              E                                        Comparative                                                                             D'       13         100/100                                                                              E                                        Example 50                                                                    Comparative                                                                             B         3         100/100                                                                              P                                        Example 51                                                                    Comparative                                                                             B         1          1/100 P                                        Example 52                                                                    Example 68                                                                              D        28         100/100                                                                              E                                        Example 69                                                                              D        32         100/100                                                                              E                                        Example 70                                                                              D'       14         100/100                                                                              E                                        Example 71                                                                              D'       14         100/100                                                                              E                                        Example 72                                                                              B'       11         100/100                                                                              E                                        Example 73                                                                              B'       12         100/100                                                                              E                                        Example 74                                                                              D        24         100/100                                                                              E                                        Example 75                                                                              B'       13         100/100                                                                              E                                        Comparative                                                                             B         1          13/100                                                                              P                                        Example 53                                                                    Comparative                                                                             B'        6         100/100                                                                              F                                        Example 54                                                                    Comparative                                                                             D'       13         100/100                                                                              F                                        Example 55                                                                    Comparative                                                                             B'        6         100/100                                                                              F                                        Example 56                                                                    Comparative                                                                             B'        4         100/100                                                                              P                                        Example 57                                                                    Comparative                                                                             B         2         100/100                                                                              E                                        Example 58                                                                    Comparative                                                                             B         1          35/100                                                                              P                                        Example 59                                                                    Comparative                                                                             B'        7          70/100                                                                              E                                        Example 60                                                                    Comparative                                                                             B         4         100/100                                                                              P                                        Example 61                                                                    ______________________________________                                               Kneading conditions                                                                                     Revolution                                            Kneader   Temperature (°C.)                                                                    number (rpm)                                 ______________________________________                                        Example 23                                                                             NVC       260           60                                           Example 24                                                                             NVC       260           60                                           Example 25                                                                             NVC       260           60                                           Example 26                                                                             NVC       260           60                                           Example 27                                                                             NVC       260           60                                           Comparative                                                                            NVC       260           60                                           Example 8                                                                     Comparative                                                                            NVC       260           60                                           Example 9                                                                     Comparative                                                                            NVC       260           60                                           Example 10                                                                    Comparative                                                                            NVC       260           60                                           Example 11                                                                    Comparative                                                                            NVC       260           60                                           Example 12                                                                    Example 28                                                                             NVC       260           60                                           Example 29                                                                             NVC       260           60                                           Example 30                                                                             NVC       260           60                                           Comparative                                                                            NVC       260           60                                           Example 13                                                                    Comparative                                                                            NVC       260           60                                           Example 14                                                                    Comparative                                                                            NVC       260           60                                           Example 15                                                                    Comparative                                                                            NVC       260           60                                           Example 16                                                                    Example 31                                                                             NVC       260           60                                           Example 32                                                                             NVC       260           60                                           Example 33                                                                             NVC       260           60                                           Example 34                                                                             NVC       260           60                                           Comparative                                                                            NVC       260           60                                           Example 17                                                                    Comparative                                                                            NVC       260           60                                           Example 18                                                                    Comparative                                                                            NVC       260           60                                           Example 19                                                                    Comparative                                                                            NVC       260           60                                           Example 20                                                                    Example 35                                                                             NVC       260           60                                           Example 36                                                                             NVC       260           60                                           Example 37                                                                             NVC       260           60                                           Example 38                                                                             NVC       260           60                                           Example 39                                                                             NVC       260           60                                           Comparative                                                                            NVC       260           60                                           Example 21                                                                    Comparative                                                                            NVC       260           60                                           Example 22                                                                    Comparative                                                                            NVC       260           60                                           Example 23                                                                    Comparative                                                                            NVC       260           60                                           Example 24                                                                    Comparative                                                                            NVC       260           60                                           Example 25                                                                    Example 40                                                                             NVC       260           60                                           Example 41                                                                             NVC       260           60                                           Example 42                                                                             NVC       260           60                                           Example 43                                                                             NVC       260           60                                           Comparative                                                                            NVC       260           60                                           Example 26                                                                    Comparative                                                                            NVC       260           60                                           Example 27                                                                    Comparative                                                                            NVC       260           60                                           Example 28                                                                    Example 44                                                                             NVC       260           60                                           Example 45                                                                             NVC       260           60                                           Example 46                                                                             NVC       260           60                                           Comparative                                                                            NVC       260           60                                           Example 29                                                                    Comparative                                                                            NVC       260           60                                           Example 30                                                                    Comparative                                                                            NVC       260           60                                           Example 31                                                                    Example 47                                                                             NVC       260           60                                           Example 48                                                                             NVC       260           60                                           Example 49                                                                             NVC       260           60                                           Example 50                                                                             NVC       260           60                                           Example 51                                                                             NVC       260           60                                           Comparative                                                                            NVC       260           60                                           Example 32                                                                    Comparative                                                                            NVC       260           60                                           Example 33                                                                    Comparative                                                                            NVC       260           60                                           Example 34                                                                    Comparative                                                                            NVC       260           60                                           Example 35                                                                    Comparative                                                                            NVC       260           60                                           Example 36                                                                    Example 52                                                                             NVC       260           60                                           Example 53                                                                             NVC       260           60                                           Example 54                                                                             NVC       260           60                                           Comparative                                                                            NVC       260           60                                           Example 37                                                                    Comparative                                                                            NVC       260           60                                           Example 38                                                                    Comparative                                                                            NVC       260           60                                           Example 39                                                                    Comparative                                                                            NVC       260           60                                           Example 40                                                                    Example 55                                                                             NVC*.sup.i                                                                              260           60                                           Example 56                                                                             NVC'      260           60                                           Example 57                                                                             NVC'      260           60                                           Example 58                                                                             NVC'      260           60                                           Comparative                                                                            NVC*.sup.j                                                                              260           60                                           Example 41                                                                    Comparative                                                                            NVC'      260           60                                           Example 42                                                                    Comparative                                                                            NVC'      260           60                                           Example 43                                                                    Comparative                                                                            NVC'      260           60                                           Example 44                                                                    Example 59                                                                             NVC       260           60                                           Example 60                                                                             NVC       260           60                                           Example 61                                                                             NVC       260           60                                           Example 62                                                                             NVC       260           60                                           Example 63                                                                             NVC       260           60                                           Comparative                                                                            NVC       260           60                                           Example 45                                                                    Comparative                                                                            NVC       260           60                                           Example 46                                                                    Comparative                                                                            NVC       260           60                                           Example 47                                                                    Comparative                                                                            NVC       260           60                                           Example 48                                                                    Comparative                                                                            NVC       260           60                                           Example 49                                                                    Example 64                                                                             NVC       260           60                                           Example 65                                                                             NVC       260           60                                           Example 66                                                                             NVC       260           60                                           Example 67                                                                             NVC       260           60                                           Comparative                                                                            NVC       260           60                                           Example 50                                                                    Comparative                                                                            NVC       260           60                                           Example 51                                                                    Comparative                                                                            NVC       260           60                                           Example 52                                                                    Example 68                                                                             NVC       260           60                                           Example 69                                                                             NVC       260           60                                           Example 70                                                                             NVC       260           60                                           Example 71                                                                             NVC       260           60                                           Example 72                                                                             NVC       260           60                                           Example 73                                                                             NVC       260           60                                           Example 74                                                                             NVC       260           60                                           Example 75                                                                             NVC       260           60                                           Comparative                                                                            NVC       260           60                                           Example 53                                                                    Comparative                                                                            NVC       260           60                                           Example 54                                                                    Comparative                                                                            NVC       260           60                                           Example 55                                                                    Comparative                                                                            NVC       260           60                                           Example 56                                                                    Comparative                                                                            NVC       260           60                                           Example 57                                                                    Comparative                                                                            NVC       260           60                                           Example 58                                                                    Comparative                                                                            NVC       260           60                                           Example 59                                                                    Comparative                                                                            NVC       260           60                                           Example 60                                                                    Comparative                                                                            NVC       260           60                                           Example 61                                                                    ______________________________________                                         *.sup.a Percentage based on the total amount of components (i) and (ii)       *.sup.b Proportion to a total of 100 parts by weight of components (i) an     (ii)                                                                          *.sup.c Notched Izod impact strength (kg · cm/cm)                    *.sup.d Visual observation                                                    *.sup.e PE1 and FAP10 previously kneaded by NVC (220° C.), blended     with PC3                                                                      *.sup.f PE1 and NMP10 previously kneaded in accordance with Example 7         *.sup.g MBS elastoner (C223, produced by Mitsubishi Rayon Co., Ltd.) adde     in an amount of 8 parts by weight based on a total of 100 parts by weight     of components (i), (ii) and (iii)                                             *.sup.h MBS elastomer (C223, produced by Mitsubishi Rayon Co., Ltd.) adde     in an amount of 8 parts by weight in accordance with Example 12               *.sup.i Crosscut adhesion test (number of squares peeled/100 squares)         *.sup.j Visual observation                                               

In accordance with the present invention, a formamide group or aformamide group and a primary amino group can be incorporated in sidechains in various high-molecular wight compounds via an imide group oran amide group. Thus, a novel copolymer can be provided which can find awide application such as a high-molecular weight amino reagent, astarting .material for functional high-molecular weight compound, astarting material for adhesives, a polymer compatibilizer, and a resinmodifier and can undergo hydrolysis to produce an active primary aminogroup.

Further, by blending a formamide group-containing copolymer containing asmall amount of a gel component with a system of a mixture of anengineering plastic and a general-purpose resin, the miscibility of thetwo components can be enhanced, and a resin composition can thus beprovided which- exhibits excellent impact resistance, particularly faceimpact strength and Izod impact strength, and excellent weatheringresistance and solvent resistance, without causing problems such aspeeling and poor external appearance.

Accordingly, the resin of the present invention can be expected to finda wide and effective application in an interior automotive trim, anoffice automation apparatus housing material, a household applicance,etc.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A copolymer or a salt thereof containing in themolecule thereof:(A) from 20 to 99.8 mole % of a recurring unitrepresented by formula (I), (B) from 50 to 0 mole % of a recurring unitrepresented by formula (II), (C) a recurring unit containing a unitrepresented by formula (III), (D) a recurring unit containing a unitrepresented by formula (IV), and (E) a recurring unit containing a unitrepresented by formula (V) in a total amount of from 60 to 0.2 mole %,provided that the amount of said recurring unit (C) is at least 0.2 mole%: ##STR8## wherein R¹ and R² each independently represents a hydrogenatom, an alkyl group having from 1 to 10 carbon atoms, a cycloalkylgroup having from 3 to 8 carbon atoms, an aryl group having from 6 to 10carbon atoms, an alkenyl group having from 2 to 4 carbon atoms, analkoxy group having from 1 to 4 carbon atoms, an alkoxycarbonyl grouphaving from 1 to 18 carbon atoms, an alkylcarbonyl group having from 1to 6 carbon atoms, an arylcarbonyl group having from 6 to 8 carbonatoms, a halogen atom a nitrile group, or ##STR9## wherein R¹³ is analkyl group having from 1 to 17 carbon atoms; R³ and R⁴ eachindependently represents a hydrogen atom, an alkyl group having from 1to 4 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms, ora halogen atom; R⁵ and R⁶ each independently represents a hydrogen atom,an alkyl group having from 1 to 6 carbon atoms, or an aryl group havingfrom 6 to 8 carbon atoms; R⁷ represents an alkylene group having from 1to 12 carbon atoms, a cycloalkylene group having from 5 to 17 carbonatoms, an arylene group having from 6 to 12 carbon atoms, anarylalkylene group having from 7 to 12 carbon atoms, or apolyoxyalkylene group having from 4 to 30 carbon atoms; R¹ to R⁷ may beeach the same or different in each of the recurring units; and X¹ and X²each independently represents NH₂ or NH--CHO.
 2. A copolymer or saltthereof as in claim 1, wherein said recurring unit (C) is a unitrepresented by the formula (III-A): ##STR10## wherein R⁵, R⁶, and R⁷ areas defined in claim 1; R⁸, R⁹, and R¹⁰ each independently represents ahydrogen atom, an alkyl group having from 1 to 10 carbon atoms, acycloalkyl group having from 3 to 8 carbon atoms, an aryl group havingfrom 6 to 10 carbon atoms, an alkenyl group having from 2 to 4 carbonatoms, an alkoxy group having from 1 to 4 carbon atoms, analkoxycarbonyl group having from 1 to 18 carbon atoms, an alkylcarbonylgroup having from 1 to 6 carbon atoms, an arylcarbonyl group having from6 to 8 carbon atoms, a halogen atom, a nitrile group, or ##STR11##wherein R¹³ is an alkyl group having from 1 to 17 carbon atoms; R¹¹ is amere bond or represents a methylene group or an ethylene group; R¹²represents a hydrogen atom or an alkyl group having from 1 to 10 carbonatoms; R⁵ to R¹² may be each the same or different in each of therecurring units; and n presents an integer of from 1 to 10, providedthat when n is 2 or more, R⁵, R⁶, and R⁷ which are each present in anumber corresponding to n may be each the same or different.
 3. Acopolymer or a salt thereof as in claim 1, wherein said recurring unit(D) is a unit represented by formula (IV-A): ##STR12## wherein R⁵, R⁶,and R⁷ are as defined in claim 1; R⁸, R⁹, and R¹⁰ each independentlyrepresents a hydrogen atom, an alkyl group having from 1 to 10 carbonatoms, a cycloalkyl group having from 3 to 8 carbon atoms, an aryl grouphaving from 6 to 10 carbon atoms, an alkenyl group having from 2 to 4carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, analkoxycarbonyl group having from 1 to 18 carbon atoms, an alkylcarbonylgroup having from 1 to 6 carbon atoms, an arylcarbonyl group having from6 to 8 carbon atoms, a halogen atom, a nitrile group, or ##STR13##wherein R¹³ is an alkyl group having from 1 to 17 carbon atoms; R¹¹ is amere bond or represents a methylene group or an ethylene group; R¹²represent a hydrogen atom or an alkyl group having from 1 to 10 carbonatoms; R⁵ to R¹² may be each the same or different in each of therecurring units; and n presents an integer of from 1 to 10, providedthat when n is 2 or more, R⁵, R⁶, and R⁷ which are each present in anumber of corresponding to n may be each the same or different.
 4. Acopolymer or a salt thereof as in claim 1, wherein said recurring unit(E) is a unit represented by formula (V-A): ##STR14## wherein R⁵, R⁶,R⁷, X¹, and X² are as defined in claim 1; R⁸, R⁹, and R¹⁰ eachindependently represents a hydrogen atom, an alkyl group having from 1to 10 carbon atoms, a cycloalkyl group having from 3 to 8 carbon atoms,an aryl group having from 6 to 10 carbon atoms, an alkenyl group havingfrom 2 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbonatoms, an alkoxycarbonyl group having from 1 to 18 carbon atoms, analkylcarbonyl group having from 1 to 6 carbon atoms, an arylcarbonylgroup having from 6 to 8 carbon atoms, a halogen atom, a nitrile group,or ##STR15## wherein R¹³ is an alkyl group having from 1 to 17 carbonatoms; R¹¹ is a mere bond or represents a methylene group or an ethylenegroup; R¹² represents a hydrogen atom or an alkyl group having from 1 to10 carbon atoms; R⁵ to R¹² may be each the same or different in each ofthe recurring units; and n presents an integer of from 1 to 10, providedthat when n is 2 or more, R⁵, R⁶, and R⁷ which are each present in anumber corresponding to n may be each the same or different.
 5. Acopolymer or a salt thereof as in claim 2, wherein said recurring unit(D) is a unit represented by formula (IV-A): ##STR16## wherein R⁵, R⁶,and R⁷ are as defined in claim 1; R⁸, R⁹, and R¹⁰ each independentlyrepresents a hydrogen atom, an alkyl group having from 1 to 10 carbonatoms, a cycloalkyl group having from 3 to 8 carbon atoms, an aryl grouphaving from 6 to 10 carbon atoms, an alkenyl group having from 2 to 4carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, analkoxycarbonyl group having from 1 to 18 carbon atoms, an alkylcarbonylgroup having from 1 to 6 carbon atoms, an arylcarbonyl group having from6 to 8 carbon atoms, a halogen atom, a nitrile group, or ##STR17##wherein R¹³ is an alkyl group having from 1 to 17 carbon atoms; R¹¹ is amere bond or represents a methylene group or an ethylene group; R¹²represent a hydrogen atom or an alkyl group having from 1 to 10 carbonatoms; R⁵ to R¹² may be each the same or different in each of therecurring units; and n presents an integer of from 1 to 10, providedthat when n is 2 or more, R⁵, R⁶, and R⁷ which are each present in anumber of corresponding to n may be each the same or different.
 6. Acopolymer or a salt thereof as in claim 5, wherein said recurring unit(E) is a unit represented by formula (V-A): ##STR18## wherein R⁵, R⁶,R⁷, X¹, and X² are as defined in claim 1; , R⁸, R⁹, and R¹⁰ eachindependently represents a hydrogen atom, an alkyl group having from 1to 10 carbon atoms, a cycloalkyl group having from 3 to 8 carbon atoms,an aryl group having from 6 to 10 carbon atoms, an alkenyl group havingfrom 2 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbonatoms, an alkoxycarbonyl group having from 1 to 18 carbon atoms, analkylcarbonyl group having from 1 to 6 carbon atoms, an arylcarbonylgroup having from 6 to 8 carbon atoms, a halogen atom, a nitrile group,or ##STR19## wherein R¹³ is an alkyl group having from 1 to 17 carbonatoms; R¹¹ is a mere bond or represents a methylene group or an ethylenegroup; R¹² represents a hydrogen atom or an alkyl group having from 1 to10 carbon atoms; R⁵ to R¹² may be each the same or different in each ofthe recurring units; and n presents an integer of from 1 to 10, providedthat when n is 2 or more, R⁵, R⁶, R⁷ which are each present in a numbercorresponding to n may be each the same or different.